Systems and methods for use of water with switchable ionic strength

ABSTRACT

Methods and systems for use of switchable water, which is capable of reversibly switching between an initial ionic strength and an increased ionic strength, is described. The disclosed methods and systems can be used, for example, in distillation-free removal of water from solvents, solutes, or solutions, desalination, clay settling, viscosity switching, etc. Switching from lower to higher ionic strength is readily achieved using low energy methods such as bubbling with C02, CS2 or COS or treatment with Bronsted acids. Switching from higher to lower ionic strength is readily achieved using low energy methods such as bubbling with air, inert gas, heating, agitating, introducing a vacuum or partial vacuum, or any combination or thereof.

This application is a § 371 Application of PCT/CA2011/050777 filed Dec. 15, 2011 which in turn claims priority to U.S. Provisional Application No. 61/522,424 filed Aug. 11, 2011, PCT/CA2011/050075 filed Feb. 10, 2011, and U.S. provisional Application No. 61/423,458 filed Dec. 15, 2010, the entire disclosure if each being incorporated herein by reference as though set forth in full.

FIELD OF THE INVENTION

The field of the invention is solvents, and specifically an aqueous solvent composition that can be reversibly converted between low ionic strength and higher ionic strength, and systems and methods of use thereof.

BACKGROUND OF THE INVENTION

Conventional solvents have fixed physical properties which can lead to significant limitations in their use as media for reactions and separations. Many chemical production processes involve multiple reactions and separation steps, and often the type of solvent that is optimum for any one step is different from that which is optimum for the next step. Thus it is common for the solvent to be removed after each step and a new solvent added in preparation for the next step. This removal and replacement greatly adds to the economic cost and environmental impact of the overall process. Therefore, there exists a need for a solvent that can change its physical properties.

Solvents are commonly used to dissolve material in manufacturing, cleaning, dyeing, extracting, and other processes. In order for a solvent to dissolve a material quickly, selectively, and in sufficient quantity, it is usually necessary for the solvent to have particular physical properties. Examples of such properties include ionic strength, hydrophobicity, hydrophilicity, dielectric constant, polarizability, acidity, basicity, viscosity, volatility, hydrogen-bond donating ability, hydrogen-bond accepting ability, and polarity. At some point in such a process after the dissolution, separation of the material from the solvent may be desired. Such a separation can be expensive to achieve, especially if the solvent is removed by distillation, which requires the use of a volatile solvent, which can lead to significant vapor emission losses and resulting environmental damage, e.g., through smog formation. Furthermore, distillation requires a large input of energy. It would therefore be desirable to find a non-distillative route for the removal of solvents from products.

Water is a particularly desirable solvent because of its low price, non-toxicity, nonflammability, and lack of adverse impact on the environment, but the separation of water from a product or other material by distillation is particularly expensive in terms of energy because of the high heat capacity of water and the high heat of vaporization of water. Therefore the need for a non-distillative route for the separation of water from products or other materials is particularly strong.

A common method for separating water from moderately hydrophobic yet water-soluble materials is “salting out”, a method in which a salt is added to an aqueous solution that includes a dissolved moderately hydrophobic compound, in sufficient amounts to greatly increase the ionic strength of the aqueous portion. High ionic strength greatly decreases the solubility of some compounds in water; thus most of the selected compound or material is forced out of the aqueous phase. The compound or material either precipitates (forms a new solid phase), creams out (forms a new liquid phase) or partitions into a pre-existing hydrophobic liquid phase if there is one. This “salting out” method requires no distillation but is not preferred because of the expense of using very large amounts of salts and, more importantly, because of the expense of removing the salt from the water afterwards.

SUMMARY OF THE INVENTION

An object of the present invention is to provide systems and methods for use of water with switchable ionic strength. In an aspect there is provided a system for switching the ionic strength of water or an aqueous solution, comprising: means for providing an additive comprising at least one nitrogen atom that is sufficiently basic to be protonated by carbonic acid; means for adding the additive to water or to an aqueous solution to form an aqueous mixture with switchable ionic strength; means for exposing the mixture with switchable ionic strength to an ionizing trigger, such as CO₂, COS, CS₂ or a combination thereof, to raise the ionic strength of the mixture; and means for exposing the mixture with raised ionic strength to i) heat, (ii) a flushing gas, (iii) a vacuum or partial vacuum, (iv) agitation, or (v) any combination thereof, to reform the aqueous mixture with switchable ionic strength. In specific embodiments, this system is used to remove water from a hydrophobic liquid or a solvent or in a desalination process.

In another aspect there is provided a system for controlling the amount, or the presence and absence, of dissolved salt in an aqueous mixture comprising a compound which reversibly converts to a salt upon contact with an ionizing trigger in the presence of water, the compound having the general formula (1):

where R¹, R², and R³ are independently:

H;

a substituted or unsubstituted C₁ to C₈ aliphatic group that is linear, branched, or cyclic, optionally wherein one or more C of the alkyl group is replaced by {—Si(R¹⁰)₂—O—} up to and including 8 C being replaced by 8 {—Si(R¹⁰)₂—O—};

a substituted or unsubstituted C_(n)Si_(m) group where n and m are independently a number from 0 to 8 and n+m is a number from 1 to 8;

a substituted or unsubstituted C₄ to C₈ aryl group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by {—Si(R¹⁰)₂—O—};

a substituted or unsubstituted aryl group having 4 to 8 ring atoms, optionally including one or more {—Si(R¹⁰)₂—O—}, wherein aryl is optionally heteroaryl;

a —(Si(R¹⁰)₂—O)_(p)— chain in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted C₁ to C₈ aliphatic and/or aryl group; or

a substituted or unsubstituted (C₁ to C₈ aliphatic)-(C₄ to C₈ aryl) group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by a {—Si(R¹⁰)₂—O—};

wherein R¹⁰ is a substituted or unsubstituted C₁ to C₈ aliphatic group, a substituted or unsubstituted C₁ to C₈ alkoxy, a substituted or unsubstituted C₄ to C₈ aryl wherein aryl is optionally heteroaryl, a substituted or unsubstituted aliphatic-alkoxy, a substituted or unsubstituted aliphatic-aryl, or a substituted or unsubstituted alkoxy-aryl groups; and

wherein a substituent is independently: alkyl; alkenyl; alkynyl; aryl; aryl-halide; heteroaryl; cycloalkyl; Si(alkyl)₃; Si(alkoxy)₃; halo; alkoxyl; amino; alkylamino; alkenylamino; amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; amidine, phosphate; phosphate ester; phosphonato; phosphinato; cyano; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfato; sulfonate; sulfamoyl; sulfonamide; nitro; nitrile; azido; heterocyclyl; ether; ester; silicon-containing moieties; thioester; or a combination thereof; and a substituent may be further substituted,

wherein when an increase in ionic strength, or the presence of salt, is desired, the compound is exposed to the ionizing trigger in the presence of water, resulting in protonation of the compound, and

wherein when a decrease in ionic strength, or the absence of salt, is desired, any ionizing trigger in said mixture is at a level that is insufficient to convert the compound to or maintain the compound in protonated form.

In a further aspect there is provided a system, comprising:

means for providing switchable water which is an aqueous liquid, comprising an additive, that has switchable ionic strength;

means for exposing the switchable water to an ionizing trigger in the presence of water thereby protonating the additive to form ionic protonated-additive, which is water-miscible or water-soluble, so that the switchable water forms an ionic aqueous liquid;

means for exposing the ionic aqueous liquid to i) heat, (ii) a flushing gas, (iii) a vacuum or partial vacuum, (iv) agitation, or (v) any combination thereof, thereby expelling the ionizing trigger from the ionic aqueous liquid which leads to deprotonation of the protonated-additive, so that the switchable water forms a non-ionic aqueous liquid; and

optionally, means for separating a selected compound from the ionic aqueous liquid prior to formation of the non-ionic aqueous liquid.

In a further aspect there is provided a system for removing a selected compound from a solid material, comprising:

means for contacting a mixture of solid material and selected compound with switchable water, which comprises a mixture of water and a switchable additive in its non-protonated, non-ionic form, so that at least a portion of the selected compound becomes associated with the switchable water to form an aqueous non-ionic solution;

optionally, means for separating the solution from residual solid material;

means for contacting the solution with an ionizing trigger in the presence of water to convert a substantial amount of the switchable additive from its unprotonated form to its protonated form, resulting in a two-phase liquid mixture having a liquid phase comprising the selected compound, and an aqueous ionic liquid phase comprising water and the ionic protonated additive; and

means for separating the selected compound from the liquid phase.

Yet another aspect provides a system for modulating an osmotic gradient across a membrane, comprising:

a semi-permeable membrane;

a switchable water comprising an additive having a switchable ionic strength on one side of said semi-permeable membrane;

means for contacting the semi-permeable membrane with feed stream; and means for contacting the switchable water with an ionizing trigger to ionize the additive and thereby increase solute concentration in the switchable water and modulate the osmotic gradient.

An aspect provides a desalination system comprising:

a semi-permeable membrane that is selectively permeable for water;

a draw solution comprising an additive having switchable ionic strength and water;

means for introducing an ionizing trigger to the draw solution to ionize the additive;

means for contacting the semi-permeable membrane with a feed stream of an aqueous salt solution to permit flow of water from the aqueous salt solution through the semi-permeable membrane into the draw solution comprising the ionized additive; and

means for separating the additive from the water.

Another aspect provides a system for concentrating a dilute aqueous solution, comprising:

a semi-permeable membrane that is selectively permeable for water;

a draw solution comprising an additive having switchable ionic strength;

means for introducing an ionizing trigger to the draw solution to ionize the additive;

means for contacting the semi-permeable membrane with a feed stream of the dilute aqueous solution to permit flow of water from the dilute aqueous solution through the semi-permeable membrane into the draw solution comprising the ionized additive; and

optionally, means for separating the additive from the water.

Another aspect provides a method of separating a solute from an aqueous solution, comprising combining in any order: water; a solute; CO₂, COS, CS₂ or a combination thereof; and an additive that comprises at least one nitrogen atom that is sufficiently basic to be protonated by carbonic acid; and allowing separation of two components: a first component that comprises an ionic form of the additive wherein the nitrogen atom is protonated and water; and a second component that comprises the solute; wherein the solute is not reactive with the additive, CO₂, COS, CS₂ or a combination thereof.

In yet another aspect, there is provided a method for modulating ionic strength, comprising providing an aqueous solution of lower ionic strength comprising water and an additive that comprises at least one nitrogen that is sufficiently basic to be protonated by carbonic acid; contacting the aqueous solution of lower ionic strength with CO₂, COS, CS₂ or a combination thereof, to form a higher ionic strength solution; subjecting the higher ionic strength solution to heat, contact with a flushing gas, or heat and contact with a flushing gas; and reforming the aqueous solution of lower ionic strength.

In an aspect, there is provided a method for destabilizing or preventing formation of a dispersion, comprising combining in any order to form a mixture: water; a water-immiscible or water-insoluble ingredient; an additive that comprises at least one nitrogen that is sufficiently basic to be protonated by carbonic acid; and CO₂, COS, CS₂ or a combination thereof; and allowing the mixture to separate into two components, a first component comprising the water-immiscible ingredient and a second component comprising water and an ionic form of the additive.

It should be understood for all aspects and embodiments thereof that include employment of an additive as described in the present application includes employment of more than one additive.

In embodiments of the above aspects, the additive is a compound of formula (1),

where R¹, R², and R³ are each independently:

H;

a substituted or unsubstituted C₁ to C₈ aliphatic group that is linear, branched, or cyclic, optionally wherein one or more C of the alkyl group is replaced by {—Si(R¹⁰)₂—O—} up to and including 8 C being replaced by 8 {—Si(R¹⁰)₂—O—};

a substituted or unsubstituted C_(n)Si_(m) group where n and m are independently a number from 0 to 8 and n+m is a number from 1 to 8;

a substituted or unsubstituted C₄ to C₈ aryl group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by a {—Si(R¹⁰)₂—O—};

a —(Si(R¹⁰)₂—O)_(p)— chain in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted C₁ to C₈ aliphatic and/or aryl group; or

a substituted or unsubstituted (C₁ to C₈ aliphatic)-(C₄ to C₈ aryl) group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by {—Si(R¹⁰)₂—O—};

wherein R¹⁰ is a substituted or unsubstituted C₁ to C₈ aliphatic group, a substituted or unsubstituted C₁ to C₈ alkoxy, a substituted or unsubstituted C₄ to C₈ aryl wherein aryl is optionally heteroaryl, a substituted or unsubstituted aliphatic-alkoxy, a substituted or unsubstituted aliphatic-aryl, or a substituted or unsubstituted alkoxy-aryl group; and wherein a substituent is independently: alkyl; alkenyl; alkynyl; aryl; aryl-halide; heteroaryl; cycloalkyl; Si(alkyl)₃; Si(alkoxy)₃; halo; alkoxyl; amino; alkylamino; dialkylamino, alkenylamino; amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; phosphate; phosphate ester; phosphonato; phosphinato; cyano; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfato; sulfonate; sulfamoyl; sulfonamide; nitro; nitrile; azido; heterocyclyl; ether; ester; silicon-containing moieties; thioester; or a combination thereof; and a substituent may be further substituted.

In certain embodiments of the above aspects, the ionic form of the additive is a compound of formula (2)

wherein R¹, R², and R³ are as defined for the compound of formula (1) above, and E is O, S or a mixture of O and S. As would be readily understood by a worker skilled in the art, under appropriate conditions the ⁻E₃CH can lose a further hydrogen atom to form ²⁻E₃C and, thereby, protonate a second additive. In a specific embodiment, the ionic form of protonated additive comprises a bicarbonate ion. In an alternative embodiment the ionic form of the additive comprises two protonated amines and a carbonate ion. Given that the acid-base reaction is an equilibrium reaction, both the carbonate ion and the bicarbonate ion can be present with the protonated additive ions.

In certain embodiments of the compounds of formulas (1) and (2), one or more of R¹, R², and R³ comprise one or more nitrogen that is sufficiently basic to be protonated by carbonic acid. As would be readily appreciated by the skilled worker, each of the one or more nitrogen that is sufficiently basic to be protonated by carbonic acid is associated with a corresponding counter ion E₃CH⁻ in the compound of formula (2).

In certain embodiments of the compounds of formulas (1) and (2), two of R¹, R², and R³, taken together with the nitrogen to which they are attached, are joined to form a heterocyclic ring. In some embodiments, the heterocyclic ring has 4 to 8 atoms in the ring. In certain embodiments of formula (1) R¹, R², and R³ may be H. R¹, R², and R³ may be a substituted or unsubstituted C₁ to C₈ alkyl group that is linear, branched, or cyclic, optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a substituted or unsubstituted C₂ to C₈ alkenyl group that is linear, branched, or cyclic, optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a substituted or unsubstituted C_(n)Si_(m) group where n and m are independently a number from 0 to 8 and n+m is a number from 1 to 8. R¹, R², and R³ may be a substituted or unsubstituted C₅ to C₈ aryl group optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a substituted or unsubstituted heteroaryl group having 4 to 8 atoms in the aromatic ring optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a —(Si(R¹⁰)₂—O)_(p)— chain in which p is from 1 to 8 which is terminated by H or a substituted or unsubstituted C₁ to C₈ alkyl group that is linear, branched, or cyclic. R¹, R², and R³ may be a substituted or unsubstituted C₁ to C₈ alkylene-C₅ to C₈ aryl group optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a substituted or unsubstituted C₂ to C₈ alkenylene-C₅ to C₈ aryl group optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a substituted or unsubstituted C₁ to C₈ alkylene-heteroaryl group having 4 to 8 atoms in the aromatic ring optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹, R², and R³ may be a substituted or unsubstituted C₂ to C₈ alkenylene-heteroaryl group having 4 to 8 atoms in the aromatic ring optionally containing 1 to 8 {—Si(R¹⁰)₂—O—}. R¹⁰ may be a substituted or unsubstituted: C₁ to C₈ alkyl, C₅ to C₈ aryl, heteroaryl having from 4 to 8 carbon atoms in the aromatic ring, or C₁ to C₈ alkoxy moiety.

In embodiments of the above aspects, the additive is a compound of formula (6),

where R¹, R², R³, and R⁴ are independently:

H;

a substituted or unsubstituted C₁ to C₈ aliphatic group that is linear, branched, or cyclic, optionally wherein one or more C of the alkyl group is replaced by {—Si(R¹⁰)₂—O—} up to and including 8 C being replaced by 8 {—Si(R¹⁰)₂—O—};

a substituted or unsubstituted C_(n)Si_(n), group where n and m are independently a number from 0 to 8 and n+m is a number from 1 to 8;

a substituted or unsubstituted C₄ to C₈ aryl group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by {—Si(R¹⁰)₂—O—};

a substituted or unsubstituted aryl group having 4 to 8 ring atoms, optionally including one or more {—Si(R¹⁰)₂—O—}, wherein aryl is optionally heteroaryl;

a —(Si(R¹⁰)₂—O)_(p)— chain in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted C₁ to C₈ aliphatic and/or aryl group; or

a substituted or unsubstituted (C₁ to C₈ aliphatic)-(C₄ to C₈ aryl) group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by a {—Si(R¹⁰)₂—O—};

wherein R¹⁰ is a substituted or unsubstituted C₁ to C₈ aliphatic group, a substituted or unsubstituted C₁ to C₈ alkoxy, a substituted or unsubstituted C₄ to C₈ aryl wherein aryl is optionally heteroaryl, a substituted or unsubstituted aliphatic-alkoxy, a substituted or unsubstituted aliphatic-aryl, or a substituted or unsubstituted alkoxy-aryl groups; and

wherein a substituent is independently: alkyl; alkenyl; alkynyl; aryl; aryl-halide; heteroaryl; cycloalkyl; Si(alkyl)₃; Si(alkoxy)₃; halo; alkoxyl; amino; alkylamino; alkenylamino; amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; amidine, phosphate; phosphate ester; phosphonato; phosphinato; cyano; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfato; sulfonate; sulfamoyl; sulfonamide; nitro; nitrile; azido; heterocyclyl; ether; ester; silicon-containing moieties; thioester; or a combination thereof; and a substituent may be further substituted.

In certain embodiments of the above aspects, the ionic form of the additive is a compound of formula (6′):

wherein R¹, R², R³ and R⁴ are as defined for the compound of formula (6) above, and E is O, S or a mixture of O and S.

In embodiments of the above aspects, the at least one nitrogen being sufficiently basic to be protonated by carbonic acid is the at least one nitrogen having a conjugate acid with a pK_(a) range from about 6 to about 14, or about 8 to about 10.

In certain embodiments of the above aspects, the additive is MDEA (N-methyl diethanol-amine); TMDAB (N,N, N′, N′-tetramethyl-1,4-diaminobutane); THEED (N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine); DMAPAP (1-[bis[3-(dimethylamino)]propyl]amino]-2-propanol); HMTETA (1,1,4,7,10,10-hexamethyl triethylenetetramine) or DIAC (N′,N″-(butane-1,4-diyl)bis(N,N-dimethylacetimidamide.

In an embodiment of certain aspects, the dilute aqueous solution is wastewater.

In certain embodiments of the aspect of a method for destabilizing or preventing formation of a dispersion, the combining in any order comprises forming a mixture by adding the additive to an aqueous solution that comprises the solute; and contacting the mixture with CO₂, COS, CS₂ or a combination thereof. In another embodiment, the combining in any order comprises forming a mixture by adding the solute to water or an aqueous solution; contacting the mixture with CO₂, COS, CS₂ or a combination thereof; and adding the additive. In yet another embodiment, the combining in any order comprises forming a mixture by adding the solute to an aqueous solution that comprises the additive; and contacting the mixture with CO₂, COS, CS₂ or a combination thereof. In another embodiment, the combining in any order comprises adding a mixture comprising the solute and the additive to an aqueous solution that comprises CO₂, COS, CS₂ or a combination thereof. In another embodiment, the combining in any order comprises forming a mixture by adding the solute to an aqueous solution that comprises CO₂, COS, CS₂ or a combination thereof, and adding the additive.

In certain embodiments of this aspect, the solute comprises a product of a chemical reaction. The first component may further comprise a water-soluble catalyst. The solute may comprise a catalyst. In another embodiment of certain aspects, combining further comprises combining the water, the solute, the additive, and the CO₂, COS, CS₂ or a combination thereof, with a hydrophobic liquid, wherein after the separating step the second component comprises the hydrophobic liquid.

In certain embodiments, a mixture of water, the solute, and the additive is a homogeneous liquid. In other embodiments, a mixture of water and the ionic form of the additive is a homogeneous liquid. In yet another embodiment, a mixture of water and the ionic form of the additive is a suspension. In another embodiment, a mixture of water and the ionic form of the additive is a solid. In certain embodiments the solute is soluble or miscible in low ionic strength aqueous solutions and is insoluble or immiscible in high ionic strength aqueous solutions.

Some embodiments further comprise isolating the first component, and subjecting it to a trigger to form an aqueous solution comprising the additive, wherein the trigger is heat, bubbling with a flushing gas, or heat and bubbling with a flushing gas. In certain embodiments, isolating includes centrifuging, decanting, filtering, or a combination thereof. In certain embodiments, the additive is water-soluble or water-miscible in both its ionized form and its non-ionized form. In certain embodiments, only the ionized form of the additive is water-soluble or water-miscible and the non-ionized form is water insoluble or immiscible.

In certain embodiments of the above aspects, number of moles of water in the aqueous solution and number of moles of basic nitrogen in the additive in the aqueous solution is approximately equivalent. In other embodiments of the above aspects, number of moles of water in the aqueous solution is in excess over number of moles of basic nitrogen in the additive in the aqueous solution.

In an embodiment of the aspect regarding a method for destabilizing or preventing formation of a dispersion, the dispersion is an emulsion and the water-immiscible ingredient is a liquid or a supercritical fluid. In other embodiments, the dispersion is a reverse emulsion and the water-immiscible ingredient is a liquid or a supercritical fluid. In yet another embodiment of this aspect, the dispersion is a foam and the water-immiscible ingredient is a gas. In other embodiments of this aspect, the dispersion is a suspension and the water-immiscible ingredient is a solid. In embodiments of the aspects described herein, a mixture may further comprise a surfactant.

In an embodiment of the aspect regarding the method for modulating ionic strength, the method is used as a sensor of CO₂, COS or CS₂; a detector of CO₂, COS or CS₂; a chemical switch; a surfactant deactivator; or to conduct electricity.

In further embodiments of the aspect regarding a method of separating a solute from an aqueous solution, the aspect regarding modulating ionic strength, and the aspect regarding a method for destabilizing or preventing formation of a dispersion are used to remove water from a hydrophobic liquid or a solvent.

In further embodiments, methods of these aspects are used in a desalination process or a wastewater treatment process.

Another aspect provides a system having a modulatable osmotic gradient across a membrane, comprising:

a semi-permeable membrane;

a switchable water located on one side of said semi-permeable membrane, said switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the osmotic pressure of the switchable water;

means for contacting the semi-permeable membrane with a feed stream on the other side of said permeable membrane; and

means for contacting the switchable water with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water and modulate the osmotic gradient across the membrane.

Another aspect provides a system for destabilization of a suspension, comprising:

a mixture of water or an aqueous solution and one or more particle solids that are substantially insoluble in water;

a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water; and

means for contacting the switchable water with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water to stop the formation of a suspension of the one or more particle solids or destabilize a suspension of the one or more fine particle solids.

Another aspect provides a method for destabilizing a suspension or preventing formation of a suspension, comprising:

combining, in any order, to form a mixture:

-   -   water or an aqueous solution and one or more particle solids         that are substantially insoluble in water;     -   an additive switchable between a first form and a second form,         wherein said second form of the additive includes at least one         ionized functional group that is neutral in said first form of         the additive; and         -   an ionizing trigger to ionize the at least one functional             group in the additive and thereby increase the ionic             strength of the mixture to stop the formation of a             suspension of the one or more particle solids or destabilize             a suspension of the one or more particle solids; and

allowing the mixture to separate into two components, a first component comprising the particle solids and a second component comprising water and an ionic form of the additive.

Another aspect provides a method for removing a solute from an aqueous solution or concentrating a dilute aqueous solution, comprising the steps of:

providing a semi-permeable membrane that is selectively permeable for water and has on one side a draw solution that is a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive;

contacting the draw solution with an ionizing trigger to switch the additive to the second form before or after association with the semi-permeable membrane, thereby increasing the osmotic pressure of the draw solution;

contacting the semi-permeable membrane with a feed stream of the aqueous solution to permit water to flow from the aqueous solution through the semi-permeable membrane into the increased ionic strength draw solution; and

optionally, removing the additive from the resulting diluted draw solution.

Another aspect provides a system and method for modulating viscosity of an aqueous solution or mixture. The system for modulating viscosity of water or an aqueous solution, comprises:

water or an aqueous solution having a first viscosity in combination with an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water; and

means for contacting the combination with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water and change the viscosity of the combination to a second viscosity.

The method for modulating viscosity comprises:

adding to the water or aqueous solution an additive that is switchable between a first form and a second form to produce a mixture, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water; and

contacting the mixture formed in step (a) with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water and change the viscosity of the mixture to a second viscosity.

Another aspect provides a system for homogeneous catalysis, comprising:

a hydrophilic catalyst;

an organic solvent;

a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water; and

means for contacting the switchable water with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water,

wherein the organic solvent is miscible with the switchable water when the additive is in the first form and immiscible or poorly miscible with the switchable water when the ionic strength is increased by switching the additive to the second form.

Another aspect provides a method for homogeneous catalysis, comprising:

forming a homogeneous reaction mixture by combining, in any order: a hydrophilic catalyst; one or more reactants; an organic solvent; water or an aqueous solution; and an additive in a first form, wherein the additive is switchable from the first form to a second form that includes at least one ionized functional group that is neutral in said first form of the additive;

allowing the reactants to react to form one or more products; and

subsequently contacting the homogeneous mixture with an ionizing trigger to switch the additive to its second form, by ionizing at least one functional group in the additive, and increase the ionic strength of the mixture to salt out the organic solvent and the one or more products,

wherein the organic solvent is miscible with water when the additive is in the first form and immiscible or poorly miscible with water when the ionic strength is increased by switching the additive to the second form.

Another aspect provides a system for modulating ionic strength of an aqueous solution comprising:

a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water; and

means for contacting the switchable water with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water,

wherein the additive is a polymer.

Another aspect provides a method for modulating the ionic strength of an aqueous solution, comprising:

contacting a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water,

wherein the additive is a polymer.

In accordance with certain embodiments of all the above aspects, the switchable water additive is a monoamine, a diamine, a triamine, a tetraamine or a polyamine, such as a polymer or a biopolymer.

In accordance with another aspect there is provided a polymer that is:

a functionalized branched or linear polyethyleneimine, such as a methylated polyethyleneimine (“MPEI”), an ethylated polyethyleneimine (“EPEI”), a propylated polyethyleneimine (“PPEI”), or a butylated polyethyleneimine (“BPEI”);

a functionalized polymethyl methacrylate (“PMMA”) based polymer, such as 3-(dimethylamino)-1-propylamine functionalized PMMA;

a functionalized polyacrylic acid (“FAA”) polymer, such as, 3-(dimethylannino)-1-propylamine functionalized FAA;

an amine-containing polyacrylic acid salt;

a functionalized poly(methyl methacrylate-co-styrene) (“PMMA/PS”), such as a 3-(dimethylamino)-1-propylamine functionalized PMMA/PS; or

a polymer synthesized form amine-containing monomers, such as a polydiethylaminoethylmethacrylate (“PDEAEMA”).

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings.

FIG. 1 shows a chemical reaction equation and a schematic of the switching reaction between differing ionic strength forms of an aqueous solution of an amine.

FIG. 2 presents the chemical structures of various tertiary amines useful as additives in the present invention.

FIG. 3 shows multiple ¹H NMR spectra from switchability study of MDEA carried out in D₂O at 400 MHz. Spectrum A was captured with no CO₂ treatment, spectrum B was captured after 20 minutes of CO₂ bubbling, and spectrum C was captured after 300 minutes of N₂ bubbling. This is discussed in Example 4 below.

FIG. 4 shows multiple ¹H NMR spectra from a switchability study of DMAE carried out in D₂O at 400 MHz. Spectrum A was captured with no CO₂ treatment, spectrum B was captured after 30 minutes of CO₂ bubbling, and spectrum C was captured after 240 minutes of N₂ bubbling. This is discussed in Example 4 below.

FIG. 5 shows multiple ¹H NMR spectra from a switchability study of HMTETA carried out in D₂O at 400 MHz. Spectrum A was captured with no CO₂ treatment, spectrum B was captured after 20 minutes of CO₂ bubbling, and spectrum C was captured after 240 minutes of N₂ bubbling. This is discussed in Example 4 below.

FIG. 6 shows multiple ¹H NMR spectra from a switchability study of DMAPAP carried out in D₂O at 400 MHz. Spectrum A was captured with no CO₂ treatment, spectrum B was captured after 20 minutes of CO₂ bubbling, and spectrum C was captured after 120 minutes of N₂ bubbling. This is discussed in Example 4 below.

FIG. 7 shows conductivity spectra for the responses of water and 1:1 v/v H₂O: DMAE; 1:1 v/v H₂O: MDEA; and 1:1 w/w H₂O: THEED solutions to a CO₂ trigger over time. This is discussed in Example 5 below.

FIG. 8 shows conductivity spectra for the responses of 1:1 v/v H₂O: DMAE; 1:1 v/v H₂O: MDEA; and 1:1 w/w H₂O: THEED solutions, which had been switched with a CO₂ trigger, to the removal of CO₂ by nitrogen bubbling over time. This is discussed in Example 5 below.

FIG. 9 shows a plot of the degree of protonation of 0.5 M solutions of DMAE and MDEA in D₂O and a 0.1 M aqueous solution of THEED in D₂O resulting from exposure to a CO₂ trigger over time. This is discussed in Example 6 below.

FIG. 10 shows a plot of the degree of deprotonation of 0.5 M solutions of DMAE and MDEA in D₂O and a 0.1 M solution of THEED in D₂O which have been switched with a CO₂ trigger to the removal of the trigger by nitrogen bubbling over time. This is discussed in Example 6 below.

FIG. 11 shows conductivity spectra for the responses of 1:1 v/v H₂O: amine solutions to a CO₂ trigger over time, in which the amine is TMDAB (♦), HMTETA (▪), and DMAPAP (▴). This is discussed in Example 7 below.

FIG. 12 shows conductivity spectra for the responses of 1:1 v/v H₂O: amine solutions, which have been switched with a CO₂ trigger, to the removal of the trigger by nitrogen bubbling over time, in which the amine is TMDAB (♦), HMTETA (▪), and DMAPAP (▴). This is discussed in Example 7 below.

FIG. 13 shows five photographs A-E representing different stages of an experiment exhibiting how the switchable ionic strength character of amine additive TMDAB can be used to disrupt an emulsion of water and n-decanol. This is discussed in Example 8 below.

FIG. 14A-C schematically depict studies performed to monitor clay settling in switchable water according to various embodiments (FIG. 14A; Study 1 of Example 12; FIG. 14B Study 2 of Example 12; and FIG. 14C Study 3 of Example 12).

FIG. 15A-D shows the results of mixing a switchable water with kaolinite clay fines and treatment with CO₂ followed by treatment with N₂ (FIG. 15A clay+1 mM TMDAB; FIG. 15B clay+1 mM TMDAB after 1 hour CO₂; FIG. 15C clay+1 mM TMDAB-CO₂ by addition of N₂ for 1 h; and FIG. 15D photographs of mixtures+TMDAB, after CO₂, and after N₂).

FIG. 16A-B shows the results of mixing a switchable water with kaolinite clay fines and treatment with CO₂ in the presence of clay (FIG. 16A clay+1 mM TMDAB after 1 hour CO₂; and FIG. 16D photographs of mixtures+TMDAB after CO₂, and after N₂).

FIG. 17A-C shows the results of mixing a CO₂ treated filtrate (obtained from a mixture of switchable water with kaolinite clay fines) with clay (FIG. 17A 1 h CO₂ filtrate+clay; FIG. 17B CO₂ blank+clay (control); FIG. 17C photographs of mixtures CO₂ filtrate+clay and CO₂ blank+clay (control)).

FIG. 18 depicts a standard system for seawater desalination using forward osmosis.

FIG. 19 depicts a system and process for desalination by forward osmosis followed by reverse osmosis using a switchable water (“SW on” refers to the bicarbonate form of the switchable water and “SW off” refers to the non-ionized form of the switchable water).

FIG. 20 depicts an alternative system and process for desalination by forward osmosis followed by removal of CO₂ (by heat or bubbling of a non-acidic gas) causing separation of much or all of the additive from the water, using a switchable water (“SW on” refers to the bicarbonate form of the switchable water and “SW off” refers to the non-ionized form of the switchable water). In such a process, if the separation of the switchable water additive from the water is incomplete, reverse osmosis or nanofiltration can be used to remove the remaining additive from the water.

FIG. 21 depicts a system that includes means for reversibly converting a non-ionized form of switchable water to an ionized form of the switchable water.

FIG. 22 depicts a system for obtaining at least one compound from a mixture of compounds using switchable water that is reversibly switched from its non-ionic form to an ionized form.

FIG. 23A shows the results of mixing a switchable water, comprising a BPEI, MW 600, switchable additive at low concentration, with montmorillonite in the absence of CO₂.

FIG. 23B shows the results of mixing a switchable water, comprising a BPEI, MW 600, switchable additive at low concentration, with montmorillonite in the presence of CO₂.

FIG. 24 shows a photograph of the results of mixing switchable water, comprising a EPEI, MW 600, switchable additive at low concentration, with montmorillonite in the absence (left) and presence (right) of CO₂.

FIG. 25 shows the results of mixing a switchable water, comprising an amine functionalized PMMA, MW 120 K, switchable additive at low concentration, with montmorillonite in the presence of CO₂.

FIG. 26A shows the results of mixing a switchable water, comprising 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (10 mol % styrene, MW=10,600-15,900) switchable additive at low concentration, with montmorillonite in the absence of CO₂.

FIG. 26B shows the results of mixing a switchable water, comprising 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (10 mol % styrene, MW=10,600-15,900) switchable additive at low concentration, with montmorillonite in the presence of CO₂.

FIG. 27 shows a photograph of the results of mixing switchable water, comprising 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) switchable additive at low concentration, with kaolinite in the absence (left) and presence (right) of CO₂.

FIG. 28A shows the results of mixing water and polyacrylamide, 6000 K, with montmorillonite in the absence of CO₂.

FIG. 28B shows esults of mixing water and polyacrylamide, 6000 K, with montmorillonite in the presence of CO₂.

FIG. 29 depicts a schematic of a method and system using switchable water in process for the hydroformylation of styrene.

FIG. 30 shows the results of hydroformylation of styrene using DMEA as a switchable water additive. (Left) All reagents mixed before reaction or CO₂ treatment. (Centre) After completion of the hydroformylation reaction. (Right) After CO₂ treatment for 45 minutes. From Top to Bottom: Cycles 1 to 3 using the same catalyst and aqueous phase.

FIG. 31 shows the settling profile of CO₂-treated kaolinite suspension in a blank, 1 mM, 10 mM, and 100 mM TMDAB solutions.

FIG. 32 graphically shows the results of mixing a switchable water, comprising a TMDAB, switchable additive, with kaolinite in the presence of CO₂.

FIG. 33 is a photograph showing the results of mixing a switchable water, comprising a TMDAB, switchable additive, with kaolinite in the presence of CO₂.

FIG. 34 shows supernatant from kaolinite settling experiment after 2 hours. From left to right: no treatment, CO₂ blank, 0.01 mM, 0.1 mM, 1 mM, 10 mM, and 100 mM TMDAB. All suspensions with TMDAB were subjected to CO₂ treatment.

FIG. 35 shows the zeta potentials of kaolinite clay particles under different treatment conditions.

FIG. 36 shows the particle size of kaolinite clay under different treatment conditions.

FIG. 37 shows the settling profile of CO₂-treated kaolinite suspension with different clay loadings.

FIG. 38 shows the effect of kaolinite clay loading on the turbidity of the supernatant water after settling in the presence of either CO₂ or both 1 mM TMDAB and CO₂.

FIG. 39 shows settling profiles of a kaolinite suspension treated with 1 mM TMDAB and CO₂ and two different controls (pH and ionic strength adjusted).

FIG. 40 shows settling profiles of a kaolinite suspension treated with 10 mM TMDAB and CO₂ and two different controls (pH and ionic strength adjusted).

FIG. 41 depicts turbidity measurements of kaolinite settling experiments with different concentrations of TMDAB and three controls (pH and ionic strength adjusted) and CO₂ blank.

FIG. 42 depicts zeta potentials of kaolinite settling experiments with different concentrations of TMDAB and three controls (pH and ionic strength adjusted) and CO₂ blank.

FIG. 43 shows chemical force titration curve showing the tip-sample adhesive force as a function of pH between an Au-coated AFM tip terminated with a SAM of 12-phenyldodecylthiol or 12-mercaptododecanoic acid and (a) silica substrate or (b) mica substrate. The forces measured between the silica substrate and the acid tip are scaled by a factor of 10 relative to other three sets of data. The error bars represent the 95% confidence interval in the adhesion force as measured from an average of at least 1000 force-distance curves.

FIG. 44 shows a schematic of a switchable surfactant (C8) in neutral form (left) and surfactant form (right).

FIG. 45 shows a schematic of a switchable amidine (C4) in the absence of CO₂ (left) and in the presence of CO₂ (right).

DETAILED DESCRIPTION OF THE INVENTION Definitions

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

As used in the specification and claims, the singular forms “a”, “an” and “the” include plural references unless the context clearly dictates otherwise.

The term “comprising” as used herein will be understood to mean that the list following is non-exhaustive and may or may not include any other additional suitable items, for example one or more further feature(s), component(s) and/or ingredient(s) as appropriate.

As used herein, “aliphatic” refers to hydrocarbon moieties that are linear, branched or cyclic, may be alkyl, alkenyl or alkynyl, and may be substituted or unsubstituted. “Alkenyl” means a hydrocarbon moiety that is linear, branched or cyclic and contains at least one carbon to carbon double bond. “Alkynyl” means a hydrocarbon moiety that is linear, branched or cyclic and contains at least one carbon to carbon triple bond. “Aryl” means a moiety including a substituted or unsubstituted aromatic ring, including heteroaryl moieties and moieties with more than one conjugated aromatic ring; optionally it may also include one or more non-aromatic ring. “C₅ to C₈ Aryl” means a moiety including a substituted or unsubstituted aromatic ring having from 5 to 8 carbon atoms in one or more conjugated aromatic rings. Examples of aryl moieties include phenyl.

“Heteroaryl” means a moiety including a substituted or unsubstituted aromatic ring having from 4 to 8 carbon atoms and at least one heteroatom in one or more conjugated aromatic rings. As used herein, “heteroatom” refers to non-carbon and non-hydrogen atoms, such as, for example, O, S, and N. Examples of heteroaryl moieties include pyridyl tetrahydrofuranyl and thienyl.

“Alkylene” means a divalent alkyl radical, e.g., —C_(f)H_(2f)— wherein f is an integer. “Alkenylene” means a divalent alkenyl radical, e.g., —CHCH—. “Alkynylene” means a divalent alkynyl radical. “Arylene” means a divalent aryl radical, e.g., —C₆H₄—. “Heteroarylene” means a divalent heteroaryl radical, e.g., —O₅H₃N—. “Alkylene-aryl” means a divalent alkylene radical attached at one of its two free valencies to an aryl radical, e.g., —CH₂—C₆H₅. “Alkenylene-aryl” means a divalent alkenylene radical attached at one of its two free valencies to an aryl radical, e.g., —CHCH—C₆H₅. “Alkylene-heteroaryl” means a divalent alkylene radical attached at one of its two free valencies to a heteroaryl radical, e.g., —CH₂—C₅H₄N. “Alkenylene-heteroaryl” means a divalent alkenylene radical attached at one of its two free valencies to a heteroaryl radical, e.g., —CHCH—C₅H₄N—.

“Alkylene-arylene” means a divalent alkylene radical attached at one of its two free valencies to one of the two free valencies of a divalent arylene radical, e.g., —CH₂—C₆H₄—. “Alkenylene-arylene” means a divalent alkenylene radical attached at one of its two free valencies to one of the two free valencies of a divalent arylene radical, e.g., —CHCH—C₆H₄—. “Alkynylene-arylene” means a divalent alkynylene radical attached at one of its two free valencies to one of the two free valencies of a divalent arylene radical, e.g., —C≡C—C₆H₄—.

“Alkylene-heteroarylene” means a divalent alkylene radical attached at one of its two free valencies to one of the two free valencies of a divalent heteroarylene radical, e.g., —CH₂—C₅H₃N—. “Alkenylene-heteroarylene” means a divalent alkenylene radical attached at one of its two free valencies to one of the two free valencies of a divalent heterarylene radical, e.g., —CHCH—C₅H₃N—. “Alkynylene-heteroarylene” means a divalent alkynylene radical attached at one of its two free valencies to one of the two free valencies of a divalent arylene radical, e.g., —C≡C—C₅H₃N—.

“Substituted” means having one or more substituent moieties whose presence does not interfere with the desired reaction. Examples of substituents include alkyl, alkenyl, alkynyl, aryl, aryl-halide, heteroaryl, cycloalkyl (non-aromatic ring), Si(alkyl)₃, Si(alkoxy)₃, halo, alkoxyl, amino, alkylamino, alkenylamino, amide, amidine, hydroxyl, thioether, alkylcarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonato, phosphinato, cyano, acylamino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azido, heterocyclyl, ether, ester, silicon-containing moieties, thioester, or a combination thereof. Preferable substituents are alkyl, aryl, heteroaryl, and ether. It is noted that aryl halides are acceptable substituents. Alkyl halides are known to be quite reactive, and are acceptable so long as they do not interfere with the desired reaction. The substituents may themselves be substituted. For instance, an amino substituent may itself be mono or independently disubstituted by further substituents defined above, such as alkyl, alkenyl, alkynyl, aryl, aryl-halide and heteroaryl cycloalkyl (non-aromatic ring).

“Short chain aliphatic” or “lower aliphatic” refers to C₁ to O₄ aliphatic. “Long chain aliphatic” or “higher aliphatic” refers to C₅ to C₈ aliphatic.

As used herein, the term “unsubstituted” refers to any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position on an atom is not specified then it is hydrogen.

As used herein, the term “polymer” means a molecule of high relative molecular mass, the structure of which essentially comprises multiple repetition of units derived from molecules of low relative molecular mass. Included within the term “polymer” are biopolymers. The term “bio-polymer,” as used herein, refers to a naturally occurring polymer. Naturally occurring polymers include, but are not limited to, proteins and carbohydrates. The term “bio-polymer” also includes derivatised forms of the naturally occurring polymers that have been modified to include one or more pendant amines. As used herein, the term “oligomer” means a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived from molecules of low relative molecular mass. A molecule can be regarded as having a high relative molecular mass if the addition or removal of one or a few of the units has a negligible effect on the molecular properties. A molecule can be regarded as having an intermediate relative molecular mass if it has molecular properties which do vary significantly with the removal of one or a few of the units. (See IUPAC Recommendations 1996 in (1996) Pure and Applied Chemistry 68: 2287-2311.)

The term “switched” means that the physical properties and in particular the ionic strength, have been modified. “Switchable” means able to be converted from a first state with a first set of physical properties, e.g., a first state of a given ionic strength, to a second state with a second set of physical properties, e.g., a state of higher ionic strength. A “trigger” is a change of conditions (e.g., introduction or removal of a gas, change in temperature) that causes a change in the physical properties, e.g., ionic strength. The term “reversible” means that the reaction can proceed in either direction (backward or forward) depending on the reaction conditions.

“Carbonated water” means a solution of water in which CO₂ has been dissolved. “CO₂ saturated water” means a solution of water in which CO₂ is dissolved to the maximum extent at that temperature.

As used herein, “a gas that has substantially no carbon dioxide” means that the gas has insufficient CO₂ content to interfere with the removal of CO₂ from the solution. For some applications, air may be a gas that has substantially no CO₂. Untreated air may be successfully employed, i.e., air in which the CO₂ content is unaltered; this would provide a cost saving. For instance, air may be a gas that has substantially no CO₂ because in some circumstances, the approximately 0.04% by volume of CO₂ present in air is insufficient to maintain a compound in a switched form, such that air can be a trigger used to remove CO₂ from a solution and cause switching. Similarly, “a gas that has substantially no CO₂, CS₂ or COS” has insufficient CO₂, CS₂ or COS content to interfere with the removal of CO₂, CS₂ or COS from the solution.

As used herein, “additive” refers to a compound comprising at least one amine or amidine nitrogen that is sufficiently basic that when it is in the presence of water and CO₂ (which form carbonic acid), for example, the amine or amidine nitrogen becomes protonated. When an aqueous solution that includes such a switchable additive is subjected to a trigger, the additive reversibly switches between two states, a non-ionized state where the nitrogen is trivalent and is uncharged, and an ionized state where the nitrogen is protonated making it a positively charged nitrogen atom. In some cases such as protonated amidines, the positive charge may be delocalized over more than one atom. For convenience herein, the uncharged or non-ionic form of the additive is generally not specified, whereas the ionic form is generally specified. The terms “ionized” or “ionic” as used herein in identifying a form the additive merely refer to the protonated or charged state of the amine or amidine nitrogen. For example, in certain examples, the additive includes other functional groups that are ionized when the amine or amidine nitrogen(s) is in the uncharged or non-ionic form.

As would be readily appreciated by a worker skilled in the art, since few protonation reactions proceed to completion, when a compound is referred to herein as being “protonated” it means that all, or only the majority, of the molecules of the compound are protonated. For example, when the additive has a single N atom, more than about 90%, or more than about 95%, or about 95%, of the molecules are protonated by carbonic acid.

As used herein, “amine additive” (see compound of formula (1) below) refers to a molecule with a structure R¹R²R³N, where R¹ through R³ are independently hydrogen or aliphatic or aryl, which includes heteroaryl, as discussed below. The ionic form of an amine (see compound of formula (2) below) is termed an “ammonium salt”. The bicarbonate salt of an amine (see compound of formula (3) below) is termed an “ammonium bicarbonate”.

As used herein, “amidine additive” refers to a molecule with a structure R¹N═C(R²)—NR³R⁴, where R¹ through R⁴ are independently hydrogen or aliphatic or aryl, which includes heteroaryl, or siloxyl, as discussed below. The ionic form of an amidine (see compound of formula (6′) below) is termed an “amidinium salt”.

As used herein, the term “a basic nitrogen” or “a nitrogen that is sufficiently basic to be protonated by carbonic acid” is used to denote a nitrogen atom that has a lone pair of electrons available and susceptible to protonation. Although carbonic acid (CO₂ in water) is mentioned, such a nitrogen would also be protonated by CS₂ in water and COS in water. This term is intended to denote the nitrogen's basicity and it is not meant to imply which of the three trigger gases (CO₂, CS₂ or COS) is used.

“Ionic” means containing or involving or occurring in the form of positively or negatively charged ions, i.e., charged moieties. “Nonionic” means comprising substantially of molecules with no formal charges. Nonionic does not imply that there are no ions of any kind, but rather that a substantial amount of basic nitrogens are in an unprotonated state. “Salts” as used herein are compounds with no net charge formed from positively and negatively charged ions. For purposes of this disclosure, “ionic liquids” are salts that are liquid below 100° C.; such liquids are typically nonvolatile, polar and viscous. “Nonionic liquids” means liquids that do not consist primarily of molecules with formal charges such as ions. Nonionic liquids are available in a wide range of polarities and may be polar or nonpolar; they are typically more volatile and less viscous than ionic liquids.

“Ionic strength” of a solution is a measure of the concentration of ions in the solution. Ionic compounds (I.e., salts), which dissolve in water will dissociate into ions, increasing the ionic strength of a solution. The total concentration of dissolved ions in a solution will affect important properties of the solution such as the dissociation or solubility of different compounds. The ionic strength, I, of a solution is a function of the concentration of all ions present in the solution and is typically given by the equation (A),

$\begin{matrix} {I = {\frac{1}{2}{\sum\limits_{i = 1}^{n}\;{c_{i}z_{i}^{2}}}}} & (A) \end{matrix}$

in which c, is the molar concentration of ion i in mol/dm³, z_(i) is the charge number of that ion and the sum is taken over all ions dissolved in the solution. In non-ideal solutions, volumes are not additive such that it is preferable to calculate the ionic strength in terms of molality (mol/kg H₂O), such that ionic strength can be given by equation (B),

$\begin{matrix} {I = {\frac{1}{2}{\sum\limits_{i = 1}^{n}\;{m_{i}z_{i}^{2}}}}} & (B) \end{matrix}$

in which m_(i) is the molality of ion i in mol/kg H₂O, and z_(i) is as defined in the previous paragraph.

A “polar” molecule is a molecule in which some separation occurs of the centres of positive and negative charge (or of partial positive and partial negative charge) within the molecule. Polar solvents are typically characterized by a dipole moment. Ionic liquids are considered to be polar solvents, even though a dipole may not be present, because they behave in the same manner as polar liquids in terms of their ability to solubilize polar solutes, their miscibility with other polar liquids, and their effect on solvatochromic dyes. A polar solvent is generally better than a nonpolar (or less polar) solvent at dissolving polar or charged molecules.

“Nonpolar” means having weak solvating power of polar or charged molecules. Nonpolar solvents are associated with either having little or no separation of charge, so that no positive or negative poles are formed, or having a small dipole moment. A nonpolar solvent is generally better than a polar solvent at dissolving nonpolar, waxy, or oily molecules.

“Hydrophobicity” is a property of a molecule leading it to be repelled from a mass of water. Hydrophobic molecules are usually nonpolar and non-hydrogen bonding. Such molecules tend to associate with other neutral and nonpolar molecules. The degree of hydrophobic character of a molecule, or hydrophobicity, can be quantified by a log P value. The log P is the logarithm of the lipid-water partition coefficient, P, of a molecule. The lipid-water partition coefficient seeks to determine the ratio of solubilities of a molecule in a lipid environment and a hydrophilic aqueous environment. The lipid-water partition coefficient is the equilibrium constant calculated as the ratio of the concentration of the molecule in the lipid phase divided by the concentration of the molecule in the aqueous phase.

“Moderately hydrophobic” is used herein to refer to compounds that are moderately or completely soluble in aqueous solutions of low ionic strength but that are much less soluble or essentially insoluble in aqueous solutions of high ionic strength. Such compound may be liquids or solids; they may be organic or inorganic. An example of a moderately hydrophobic compound is tetrahydrofuran.

Partition coefficients can be determined using n-octanol as a model of the lipid phase and an aqueous phosphate buffer at pH 7.4 as a model of the water phase. Because the partition coefficient is a ratio, it is dimensionless. The partition coefficient is an additive property of a molecule, because each functional group helps determine the hydrophobic or hydrophilic character of the molecule. If the log P value is small, the molecule will be miscible with (or soluble in) water such that the water and molecule will form a single phase in most proportions. If the log P value is large, the compound will be immiscible with (or insoluble in) water such that a two-phase mixture will be formed with the water and molecule present as separate layers in most proportions.

It is possible to theoretically calculate log P values for many organic compounds because of the additive nature of the partition coefficient arising from the individual functional groups of a molecule. A number of computer programs are available for calculating log P values. The log P values described herein are predicted using ALOGPS 2.1 software, which calculates the log P value for a given molecule using nine different algorithms and then averages the values. This computational method is fully described by Tetko I. V. and Tanchuk V. Y. in J. Chem. Inf. Comput. Sci., 2002, 42, 1136-1145 and in J. Comput. Aid. Mol. Des., 2005, 19, 453-463, both of which are incorporated herein by reference.

In contrast to hydrophobicity, “hydrophilicity” is a property of a molecule allowing it to be dissolved in or miscible with a mass of water, typically because the molecule is capable of transiently bonding with water through hydrogen bonding. Hydrophilic molecules are usually polar. Such molecules may thus be compatible with other polar molecules. Hydrophilic molecules may comprise at least one hydrophilic substituent which can transiently bond with water through hydrogen bonding. Hydrophilic substituents include amino, hydroxyl, carbonyl, carboxyl, ester, ether and phosphate moieties.

“Insoluble” refers to a poorly solubilized solid in a specified liquid such that when the solid and liquid are combined a heterogeneous mixture results. It is recognized that the solubility of an “insoluble” solid in a specified liquid might not be zero but rather it would be smaller than that which is useful in practice. The use of the terms “soluble”, “insoluble”, “solubility” and the like are not intended to imply that only a solid/liquid mixture is intended. For example, a statement that the additive is soluble in water is not meant to imply that the additive must be a solid; the possibility that the additive may be a liquid is not excluded.

“Miscibility” is a property of two liquids that when mixed provide a homogeneous solution. In contrast, “immiscibility” is a property of two liquids that when mixed provide a heterogeneous mixture, for instance having two distinct phases (i.e., layers).

As used herein, “immiscible” means unable to merge into a single phase. Thus two liquids are described as “immiscible” if they form two phases when combined in a proportion. This is not meant to imply that combinations of the two liquids will be two-phase mixtures in all proportions or under all conditions. The immiscibility of two liquids can be detected if two phases are present, for example via visual inspection. The two phases may be present as two layers of liquid, or as droplets of one phase distributed in the other phase. The use of the terms “immiscible”, “miscible”, “miscibility” and the like are not intended to imply that only a liquid/liquid mixture is intended. For example, a statement that the additive is miscible with water is not meant to imply that the additive must be a liquid; the possibility that the additive may be a solid is not excluded.

As used herein, the term “contaminant” refers to one or more compounds that is intended to be removed from a mixture and is not intended to imply that the contaminant has no value.

As used herein, the term “salt” refers to an ionic compound that is not a zwitterion. This may include sodium chloride (traditional table salt), other inorganic salts, or salts in which the anion(s), the cation(s), or both are organic. The term “salty” means comprising at least one salt.

As used herein the term “emulsion” means a colloidal suspension of a liquid in another liquid. Typically, an emulsion refers a suspension of hydrophobic liquid (e.g., oil) in water whereas the term “reverse emulsion” refers to a suspension of water in a hydrophobic liquid.

As used herein the term “suspension” means a heterogeneous mixture of fine solid particles suspended in liquid.

As used herein the term “foam” means a colloidal suspension of a gas in a liquid.

As used herein the term “dispersion” means a mixture of two components, wherein one component is distributed as particles, droplets or bubbles in the other component, and is intended to include emulsion (i.e., liquid in liquid, liquid in supercritical fluid, or supercritical fluid in liquid), suspension (i.e., solid in liquid) and foam (i.e., gas in liquid).

“NMR” means Nuclear Magnetic Resonance. “IR spectroscopy” means infrared spectroscopy. “UV spectroscopy” means ultraviolet spectroscopy.

The term “DBU” means 1,8-diazabicyclo-[5.4.0]-undec-7-ene. The term “DMAE” means N,N-(dimethylamino)ethanol. The term “MDEA” means N-methyl diethanol-amine. The term “TMDAB” means N,N,N′,N′-tetramethyl-1,4-diaminobutane. The term “TEDAB” means N,N,N′,N′-tetraethyl-1,4-diaminobutane. The term “THEED” means N,N,N′,N′-tetrakis(2-hydroxyethyl) ethylenediamine. The term “DMAPAP” means 1-[bis[3-(dimethylamino)]propyl]amino]-2-propanol. The term “HMTETA” means 1,1,4,7,10,10-hexamethyl triethylenetetramine. Structural formulae for these compounds are shown in FIG. 2.

The term “wastewater” means water that has been used by a domestic or industrial activity and therefore now includes waste products.

As used herein, “PEI” means branched or linear polyethyleneimines of various molecular weights, including, but not limited to, methylated polyethyleneimine (“MPEI”) ethylated polyethyleneimine (“EPEI”), propylated polyethyleneimine (“PPEI”), and butylated polyethyleneimine (“BPEI”).

As used herein, “PMMA” refers to polymethyl methacrylate based polymers including, but not limited to, 3-(dimethylamino)-1-propylamine functionalized PMMA of various molecular weights.

As used herein, “PAA” refers to polyacrylic acid based polymers including, but not limited to, 3-(dimethylamino)-1-propylamine functionalized PAA of various molecular weights.

As used herein, “PMMA/PS” refers to poly(methyl methacrylate-co-styrene), which may be functionalized with, for example, 3-(dimethylamino)-1-propylamine.

US Patent Application Publication No. 2008/0058549 discloses a solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, such as CO₂. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol or a combination thereof.

Zhou K., et al, “Re-examination of Dynamics of Polyelectrolytes in Salt-Free Dilute solutions by Designing and Using a Novel Neutral-Charged-Neutral Reversible Polymer” Macromolecules (2009) 42, 7146-7154, discloses a polymer that can undergo a neutral-charged-neutral transition in DMF with 5% water. The transition between the neutral and charged state is achieved by alternately bubbling CO₂ and N₂ through a mixture containing the polymer.

Switchable Water

Provided herein is a liquid mixture comprising an aqueous component in which the ionic strength can be reversibly varied from a lower ionic strength to a higher ionic strength by subjecting the mixture to a trigger. Put simply, such aspects provide water that can be reversibly switched between water-with-substantially-no-salt and salty-water, over and over with little or substantially no energy input. The term “switchable water” is used herein to refer to the aqueous component which is pure water mixed with an additive, or an aqueous solution mixed with an additive, wherein the additive can switch between an ionic form and a non-ionic form in order to increase or decrease the ionic strength of the water or aqueous solution, respectively.

Traditionally, once a salt was added to water, high energy input was required to recapture the water (e.g., since the salted water had to be heated to its boiling point). Accordingly, certain aspects of this application provide methods of separating a compound from a mixture by solubilizing the compound in an aqueous solution of a first ionic strength (a switchable water) and then isolating the compound by switching the medium to a solution of a second ionic strength. Such methods use non-ionic aqueous solutions and ionic liquids. Switchable water can be reused over and over in the extraction of a desired or selected compound.

Aqueous mixtures including switchable water as described herein are useful for extraction of a solute from a mixture, a solution, or a matrix. After use in its lower ionic strength form for example, for extraction of a water soluble solute, the switchable water is triggered to switch to its higher ionic strength form, to cause the precipitation or separation of the solute. The switchable water can then be re-used by switching it back to the lower ionic strength form. Solutes for extraction are either pure compounds or mixtures of compounds. They include both contaminants and desired materials. Such solutes can be extracted from various compositions, including, without limitation, soil, clothes, rock, biological material (for example, wood, pulp, paper, beans, seeds, meat, fat, bark, grass, crops, fur, natural fibres, cornstalks, oils), water, equipment, or manufactured materials (for example, machined parts, molded parts, extruded material, chemical products, refined oils, refined fuels, fabrics, fibres, sheets, and like materials, whether made of metal, mineral, plastic, inorganic, organic, or natural materials or combinations thereof). Desired solutes to be extracted include, without limitation, medicinal compounds, organic compounds, intermediate compounds, minerals, synthetic reagents, oils, sugars, foods, flavorants, fragrances, dyes, pesticides, fungicides, fuels, spices, and like materials.

Other non-limiting examples of selected solutes include the following: plant extracts (e.g., lignin, cellulose, hemicellulose, pyrolysis products, leaf extracts, tea extracts, petal extracts, rose hip extracts, nicotine, tobacco extracts, root extracts, ginger extracts, sassafras extracts, bean extracts, caffeine, gums, tannins, carbohydrates, sugars, sucrose, glucose, dextrose, maltose, dextrin); other bio-derived materials (e.g., proteins, creatines, amino acids, metabolites, DNA, RNA, enzymes); alcohols, methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol, 2-butanol, t-butanol, 1,2-propanediol, glycerol, and the like; products of organic synthesis (e.g., ethylene glycol, 1,3-propanediol, polymers, poly(vinyl alcohol), polyacrylamides, poly(ethylene glycol), poly(propylene glycol)); industrially useful chemicals (e.g., plasticizers, phenols, formaldehyde, paraformaldehyde, surfactants, soaps, detergents, demulsifiers, anti-foam additives); solvents (e.g., THF, ether, ethyl acetate, acetonitrile, dimethylsulfoxide, sulfolene, sulfolane, dimethylformamide, formamide, ethylene carbonate, propylene carbonate, dimethylacetamide, hexamethylphosphoramide); fossil fuel products (e.g., creosote, coal tar, coal pyrolysis oil components, crude oil, water-soluble components of crude oil); colorants (e.g., dyes, pigments, organic pigments, stains, mordants); undesired compounds and mixtures (e.g., dirt or stains on clothing or equipment).

Selected compounds that may be suited to extraction methods described herein include compounds that are soluble to different degrees in water of lower ionic strength and water of higher ionic strength. Certain selected solutes are more soluble in aqueous solutions as described herein that have lower ionic strength and include an amine additive than they are in neat water. Because the following description is about a reversible reaction that proceeds from low ionic strength to high ionic strength and back again, over and over, one must choose one of these two states to begin the process. However, this choice is arbitrary, and as described below, one could start with either state depending on the specific application.

Switchable Additive

The exemplary description provided below starts with the low ionic strength switchable water, which comprises water and a switchable additive in its non-ionic form that is substantially soluble in water. The switchable water with the non-ionic form of the additive has a lower ionic strength than the switchable water with the ionic form of the additive. In specific embodiments, where the switchable additive does not contain other ionized functional groups, the switchable water with the non-ionic form of the additive has little to no ionic strength.

The switchable water can be used as a solvent to dissolve compounds that do not react with the additive. When it is desirable to separate dissolved compounds from the non-ionic switchable water, a trigger is applied and the additive is converted to its ionic form. The resultant ionic switchable water has a higher ionic strength.

In accordance with one example, both the non-ionic and the ionic forms of the switchable additive employed in this reversible reaction are soluble with water, such that where a liquid mixture separates into two phases, a hydrophobic phase and an aqueous phase, substantially all of the additive remains in the aqueous layer, no matter whether it is in its non-ionic form or its ionic form. In this example, in contrast to the additive, certain compounds will no longer be soluble in the higher ionic strength solution, and they will separate into a phase that is distinct from the ionic aqueous phase. This distinct phase may be a pre-existing hydrophobic liquid phase (non-aqueous solvent).

In accordance with an alternative example, only the ionic form of the switchable additive is substantially soluble in water, such that when the additive is converted to its non-ionic form, two phases are formed, with the non-ionic form of the additive being largely or completely in the non-aqueous phase. The non-aqueous phase can include only the non-ionic form of the switchable additive, or it can include a solvent that is not soluble or miscible with water, such as a pre-existing hydrophobic liquid phase (non-aqueous solvent). In many cases, the non-aqueous phase will comprise some water, although in many applications the amount of water in the non-aqueous phase would preferably be as low as possible.

The switchable additive (also referred to herein as an “additive”) is a compound comprising an amine nitrogen that is sufficiently basic that when it is in the presence of water and CO₂ (which form carbonic acid), for example, it becomes protonated. When an aqueous solution that includes such a switchable additive is subjected to a trigger, the additive reversibly switches between two states, a non-ionic state where the amine nitrogen is trivalent and is uncharged, and an ionic state where the amine nitrogen is protonated making it a 4-coordinate positively charged nitrogen atom. Accordingly, the charged amine moiety has a negatively charged counterion that is associated with it in solution. The nature of the counterion depends on the trigger used and will be described below. An aqueous solution comprising the additive in its ionic state is distinguishable from an aqueous solution comprising the compound in its non-ionic state by comparing the ionic strengths.

The switchable additive is at least partially soluble in water when in its ionic form. Specifically, the switchable additive must be sufficiently soluble in water when in its ionic form to impart an increase in ionic strength in comparison to the ionic strength of the water (or aqueous solution depending on the application) without the ionic form of the additive present.

In certain embodiments, the switchable water comprises water and an amine additive that is peralkylated. The term “peralkylated” as used herein means that the amine has alkyl or other groups connected to nitrogen atoms that are sufficiently basic that they are protonated by carbonic acid, so that the molecule contains no N—H bonds. Amine compounds of formulae (1) and (4) which do not have any N—H bonds are preferred because most primary and secondary amines are capable of carbamate formation during switching with CO₂. Removal of carbamate ions in water by heating and bubbling with a flushing gas to switch the salt back to the amine form can be difficult. This is evident from comparative example 2, in which it was determined that it was not possible to switch certain primary and a secondary amine additives in ionic form back to the corresponding non-ionic amine forms using low energy input triggers. Thus, carbamate formation is undesirable because it can decrease the efficiency of reverting an ionic solution back to an aqueous solution of amine (non-ionic form). This concern about formation of carbamate ions is not relevant if the amine is an aniline (i.e., an aryl or heteroaryl group is attached directly to a nitrogen atom); in such a molecule, an N—H bond is not considered unpreferred.

Stable carbamate formation can be greatly reduced by using bulky substituents on primary and secondary amines to provide steric hindrance (Bougie F. and Illiuta M. C., Chem Eng Sci, 2009, 64, 153-162 and references cited therein). Steric hindrance allows for easier CO₂ desorption. Tertiary amines are preferred since their ionic forms do not include carbamates but rather are bicarbonates anions. However, in some embodiments, primary and secondary amines that have bulky substituents are preferred because the switching process may be faster than that observed with tertiary amines. As demonstrated in Example 22 below, the inventors reasonably expect that efficient reversible switching is possible between non-ionic and ionic forms with primary and secondary amines that have bulky substituents. The inventors also reasonably expect that the presence of a small amount of a secondary or primary amine that is capable of carbamate formation, in addition to a switchable additive compound of formula (1), would not inhibit switching of the additive. In some embodiments, the presence of a small amount of secondary or primary amine may increase the rate of switching of the additive between its ionic and non-ionic forms.

In one embodiment, a primary amine additive can be used. However, the reversion of the ionic form of the primary amine additive to the non-ionic form is too difficult to be of practical use in application where reversion is required. Rather, a primary amine additive can be valuable in situations in which reversal of the additive ionization is unnecessary. Alternatively, a primary amine additive can be valuable in situations in which the use of higher temperatures, longer reaction times or other more severe conditions to force the reversion to take place are acceptable.

In another embodiment, a secondary amine additive can be used. As demonstrated in Example 22, certain secondary amine additives are reversibly switchable between an ionized and a non-ionized form.

Useful additives can comprise more than one nitrogen centre. Such compounds are called, for example, diamines, triamines, tetraamines or polyamines. Polyamines include polymers with nitrogens in the polymer backbone. Polyamines also include polymers with nitrogens in pendant groups, for example, biopolymers and derivatives thereof. Polyamines also include polymers with nitrogens in the polymer backbone and with nitrogens in pendant groups. Polyamines also include small molecules (i.e., not polymers) that have more than one nitrogen atom. Examples of polyamines include poly(vinylamine), poly(N-vinyl-N,N-dimethylamine), poly(allylamine) poly(N-allyl-N,N-dimethylamine), 1,2,3,4,5,6-hexakis(N,N-dimethylaminomethyl)benzene (e.g., C₆(CH₂NMe₂)₆) and 1,2,3,4,5,6-hexakis(N,N-dimethylaminomethyl)cyclohexane (e.g., C₆H₆(CH₂NMe₂)₆).

In a specific example, the additive is a biopolymer comprising one or more amine nitrogens that are sufficiently basic that when in the presence of water and CO₂ (which form carbonic acid), for example, it becomes protonated. Examples of suitable biopolymers for use as a switchable additive include, but are not limited to, collagens (including Types I, II, III, IV, V and VI), denatured collagens (or gelatins), fibrin-fibrinogen, elastin, glycoproteins, polysaccharides such as, but not limited to, alginate, chitosan, N-carboxymethyl chitosan, O-carboxymethyl chitosan, N,O-carboxymethyl chitosan, hyaluronic acid, chondroitin sulphates and glycosaminoglycans (or proteoglycans), oxidized polysaccharides such as, but not limited to oxidized chondroitin sulphate, oxidized alginate and oxidized hyaluronic acid. In each case, the biopolymer can be derivatised to incorporate amine nitrogens that are sufficiently basic that when in the presence of water and CO₂ (which form carbonic acid), for example, it becomes protonated.

An example of a method to prepare polyamine additive includes reacting homopolymers of propylene oxide or ethylene oxide with maleic anhydride under free radical conditions either in solution or in solid state to yield grafted material. As an alternative to homopolymers, random or block copolymers of propylene oxide and ethylene oxide can be used. Once prepared, the grafted material is reacted with a diamine (e.g., 3-dimethylamino-1-propylamine) to form a polyamine additive that is useful as an additive in embodiments of the invention described herein. In some embodiments, ratios of the ethylene oxide and propylene oxide repeating units of the polyamine are controlled such that, at a given temperature and pressure, the additive in its “off” state is substantially insoluble in water and in its “on” state is soluble in water.

Another example of a method to prepare polyamine additive includes reacting a polymer of acrylic acid (or a corresponding ester) with a diamine (e.g., 3-dimethylamino-1-propylamine) to form the additive via amide bond formation. As an alternative to acrylic acid polymer, another polymer that comprises carboxylic acid (or a corresponding ester thereof) can be used. An example of such a polymer includes a random or block co-polymer of polystyrene and a polymer comprising carboxylic acid and/or ester. The amide bond is formed, for example, via dehydration, alcohol elimination, alkoxide elimination, acid chloride reaction, catalytically, or the like. Any secondary or primary amide nitrogen atom can be alkylated to further tune solubility properties of the additive. In some embodiments, ratios of the components of the polyamine are controlled such that, at a given temperature and pressure, the additive in its “off” state is substantially insoluble in water and in its “on” state, after exposure to CO₂ and H₂O, is soluble in water.

Specific, non-limiting examples of amine containing polymers useful as switchable water additives are: branched or linear polyethyleneimines (“PEIs”) of various molecular weights, including, functionalized PEIs such as, methylated polyethyleneimine (“MPEI”), ethylated polyethyleneimine (“EPEI”), propylated polyethyleneimine (“PPEI”), and butylated polyethyleneimine (“BPEI”); functionalized polymethacrylate (“PMA”) polymers of various molecular weights; functionalized poly(methyl acrylate) (“PMeA”) polymers of various molecular weights; functionalized polymethyl methacrylate (“PMMA”) polymers including, but not limited to, 3-(dimethylamino)-1-propylamine functionalized PMMA of various molecular weights; functionalized polyacrylic acid (“PAA”) polymers including, but not limited to, 3-(dimethylamino)-1-propylamine functionalized PAA of various molecular weights; and functionalized poly(methyl methacrylate-co-styrene) (“PMMA/PS”) copolymers including, but not limited to 3-(dimethylamino)-1-propylamine functionalized PMMA/PS of various molecular weights and mol % styrenic units. The term “functionalized”, as used herein with reference to polymers, means polymers that comprise one or more functional groups, such as, but not limited to, substituted or unsubstituted aliphatic groups. In certain embodiments the polymers are functionalized to include protonatable nitrogen atoms. As would be well understood by a worker skilled in the art, a functionalized polymer can be synthesized by functionalizing a polymer at pendant reactive groups (e.g., acid groups) to add the desired functional group or groups. In a specific example of this alternative, polymers are further functionalized at existing primary amines to form secondary or tertiary amines. Alternatively, the functionalized polymer can be synthesized from monomers, or mixture of monomers, that contain the desired functional group or groups.

When referring to polymers herein, the terminology used refers to “functionalized” polymers without specifying the bonds formed as a result of incorporation of the functional groups in the polymer. For example, the polyacrylamide formed from the reaction of a PAA with an amine is, for simplicity, referred to herein as a “functionalized PAA”.

In certain embodiments the additive is immiscible or insoluble, or poorly miscible or poorly soluble, in water but is converted by a trigger to a form that is ionic and is at least partially soluble or miscible with water. In order to function as a switchable additive, the additive must be sufficiently soluble in water or an aqueous solution when in the “on” or “ionized form” so that the ionized additive imparts an increase in ionic strength of the water or aqueous solution without the additive or with the additive in the “off” or “non-ionized” form. The immiscibility or insolubility of the additive in its non-ionized form is advantageous in some applications because the additive can be readily removed from the water, when such removal is desired, by the removal of the trigger. TEDAB is an example of an additive that functions according to this embodiment.

Also provided herein are ionic polymers, which are salts formed from a simple acid-base reaction between a polymer having pendant acidic groups and amine or amidine-containing molecules having an accessible basic group (for example a diamine- or triamine-containing compound). The “non-ionized”, or “off” form of these ionic polymers is actually partially ionized, which can result in increase water solubility of the “non-ionized” form of these polymers, in comparison to the non-ionized form of the functionalized polymers described above. For example, a basic diamine can undergo an acid-base reaction with a polymer containing an acidic side group to yield a singly ionic polymer in the off form. This polymer can then undergo a second reaction with carbonic acid, for example, to give a doubly ionic polymer in the on form.

In certain embodiments, the water solubility or miscibility of a polymeric additive in water can be switched by taking advantage of the upper and/or lower critical solution temperatures of the polymeric additive. In the present situation the lower critical solution temperature (or LCST) is the critical temperature below which the polymer is soluble or miscible in water or an aqueous solution and the upper critical solution temperature (or UCST) is the critical temperature above which the polymer is soluble or miscible in water. For those polymeric additives that have an LCST in the non-ionized form, temperature can be used to facilitate removal of the additive from water. After the polymeric additive is switched from its ionized form to its non-ionized form, the temperature is raised to above the LOST such that the polymeric additive either precipitates or becomes immiscible with the water or aqueous solution of the system. The polymeric additive can then be removed from the water using standard techniques such as filtration or decanting.

In certain aspects the additive is a compound of formula (1),

where R¹, R², and R³ are independently:

H;

a substituted or unsubstituted C₁ to C₈ aliphatic group that is linear, branched, or cyclic, optionally wherein one or more C of the alkyl group is replaced by a {—Si(R¹⁰)₂—O—} unit up to and including 8 C units being replaced by 8 {—Si(R¹⁰)₂—O—} units;

a substituted or unsubstituted C_(n)Si_(m) group where n and m are independently a number from 0 to 8 and n+m is a number from 1 to 8;

a substituted or unsubstituted C₄ to C₈ aryl group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by a {—Si(R¹⁰)₂—O—} unit;

a substituted or unsubstituted aryl group having 4 to 8 ring atoms, optionally including one or more {—Si(R¹⁰)₂—O—} unit, wherein aryl is optionally heteroaryl;

a —(Si(R¹⁰)₂—O)_(p)— chain in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted C₁ to C₈ aliphatic and/or aryl group;

a substituted or unsubstituted C₁ to C₈ aliphatic-C₄ to C₈ aryl group wherein aryl is optionally heteroaryl, optionally wherein one or more C is replaced by a {—Si(R¹⁰)₂—O—} unit; or

wherein R¹⁰ is a substituted or unsubstituted C₁ to O₈ aliphatic group, C₁ to O₈ alkoxy, or C₄ to C₈ aryl wherein aryl is optionally heteroaryl.

A substituent may be independently: alkyl; alkenyl; alkynyl; aryl; aryl-halide; heteroaryl; cycloalkyl (non-aromatic ring); Si(alkyl)₃; Si(alkoxy)₃; halo; alkoxyl; amino, which includes diamino; alkylamino; alkenylamino; amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; phosphate; phosphate ester; phosphonato; phosphinato; cyano; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfato; sulfonate; sulfamoyl; sulfonamide; nitro; nitrile; azido; heterocyclyl; ether; ester; silicon-containing moieties; thioester; or a combination thereof. The substituents may themselves be substituted. For instance, an amino substituent may itself be mono or independently disubstituted by further substituents defined above, such as alkyl, alkenyl, alkynyl, aryl, aryl-halide and heteroaryl cyclyl (non-aromatic ring).

A substituent may be preferably at least one hydrophilic group, such as Si(C₁-C₄-alkoxy)₃, C₁-C₄-alkoxyl, amino, C₁-C₄-alkylamino, C₂-C₄-alkenylamino, substituted-amino, C₁-C₄-alkyl substituted-amino, C₂-C₄-alkenyl substituted-amino amide, hydroxyl, thioether, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkoxycarbonyloxy, carbonate, C₁-C₄-alkoxycarbonyl, aminocarbonyl, C₁-C₄-alkylthiocarbonyl, phosphate, phosphate ester, phosphonato, phosphinato, acylamino, imino, sulfhydryl, C₁-C₄-alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, C₁-C₄-alkoxy-C₁-C₄-alkyl, silicon-containing moieties, thioester, or a combination thereof.

In some embodiments, compounds of formula (1) are water-soluble or water-miscible. In alternative embodiments, compounds of formula (1) are water-insoluble or water-immiscible, or only partially water-soluble or water-miscible.

In certain embodiments, each of R¹, R² and R³ may be substituted by a tertiary amine, which is optionally sufficiently basic to become protonated when it is in the presence of water and CO₂ (which form carbonic acid).

The present application further provides an ionic solution comprising water and a salt additive of formula (2) where R′, R², and R³ are as defined for the compound of formula (1) and E is O, S or a mixture of O and S,

In some embodiments, a compound of formula (2) is prepared by a method comprising contacting a compound of formula (1) with CO₂, CS₂ or COS in the presence of water, thereby converting the compound to the salt of formula (2). In some embodiments, a compound of formula (2) is water soluble.

Any of R¹, R², and R³ of the salt of formula (2) may be optionally substituted as discussed for the compound of formula (1). However, should the optional substituent comprise a nitrogen of sufficient basicity to be protonated by carbonic acid, it can be present in its protonated form as it may be protonated by the ionizing trigger. For instance, if the optional substituent is an amino group, such as a tertiary amino group, this may exist as a quaternary ammonium moiety in the salt of formula (2).

The present application further provides a switchable water comprising water and a salt of formula (3). In a preferred embodiment, in the presence of water and CO₂, an amine compound of formula (1), converts to an ammonium bicarbonate, depicted as a salt of formula (3) as shown below

where R¹, R², and R³ areas defined above. In some embodiments, a compound of formula (3) is water soluble. There may be some carbonate anions present, in addition to bicarbonate anions. As would be readily understood by a worker skilled in the art, under appropriate conditions the ⁻O₃CH can lose a further hydrogen atom to form ²⁻O₃C (carbonate) and, thereby, protonate a second additive. In a specific embodiment, the ionic form of protonated additive comprises a bicarbonate ion. In an alternative embodiment the ionic form of the additive comprises two protonated amines and a carbonate ion. Given that the acid-base reaction is an equilibrium reaction, both the carbonate ion and the bicarbonate ion may be present with protonated additive ions.

Should an optional substituent comprise a basic nitrogen, it may be present in protonated form if it can be protonated by carbonic acid. For instance, if the optional substituent is an amino group, such as a tertiary amino group, this may exist as a quaternary ammonium moiety in the salt of formula (3).

A water-soluble additive of formula (1) can provide a switchable water that is a single-phase mixture and can function as a solvent for water-soluble substances. Although in theory an aqueous solution of the water-soluble compound of formula (1), in the absence of other components, will have an ionic strength of zero since no charged species are present; in practice, the ionic strength might be small but higher than zero due to some impurities such as dissolved air or small amounts of salts. Because of the zero or small ionic strength, a switchable water comprising a water-miscible compound of formula (1) is particularly useful as a solvent for substances which are miscible or soluble in low ionic strength aqueous solutions.

In some embodiments, both the non-ionic additive of formula (1) and the salt additive formula (2) are water-soluble and can each, therefore, form a single phase aqueous solution when dissolved in water. This means that the non-ionic compound of formula (1) and the salt of formula (2) can remain in aqueous solution as a single phase with water after switching. Switching a non-ionic switchable water comprising the compound of formula (1) to an ionic switchable water comprising the salt of formula (2) increases the ionic strength of the switchable water. Increasing the ionic strength of the switchable water can be used to expel a dissolved substance which is insoluble in such an increased ionic strength solution without the need for distillation or other energy intensive separation techniques.

Alternatively water-insoluble, or poorly soluble, additive of formula (1) can provide a switchable water that is a two-phase mixture. Although in theory the water in the two-phase mixture, in the absence of other components, will have a zero or very low ionic strength because no charged species are present in significant quantities (charged species present in small concentrations may include the H⁺ and OH⁻ ions that one would expect from the dissociation of water and the amount of protonated additive formed by the reaction of additive with water); in practice, the ionic strength might also be slightly increased by the presence of some impurities such as dissolved air or small amounts of salts. Because of the zero or small ionic strength, a switchable water mixture comprising a water-immiscible, or poorly miscible additive of formula (1) is particularly useful as a solvent for substances which are miscible or soluble in low ionic strength aqueous solutions.

In some embodiments, the non-ionic additive of formula (1) is water-insoluble, or poorly soluble, and the salt additive formula (2) is water-soluble such that a single phase is formed only when the additive is switched to its ionic form. Switching a non-ionic switchable water comprising the compound of formula (1) to an ionic switchable water comprising the salt of formula (2) increases the ionic strength of the switchable water. In this embodiment, the fact that the non-ionic form of the additive is water-insoluble or immiscible, can be useful in situations where it is beneficial to remove the additive from the aqueous phase following switching to the non-ionic form.

In accordance with either embodiment, the salt of formula (2) can be switched back into a non-ionic additive of formula (1) by removal of the ionizing trigger, such as CO₂, or by addition of a non-ionizing trigger. This is advantageous because it allows the re-use of the switchable water.

In certain embodiments, at least one of R¹, R² and R³ can be replaced by one or more further tertiary amine groups. For instance, R¹ may be substituted with a tertiary amine, which may itself be further substituted with a tertiary amine. Thus, the present invention includes the use of an aqueous solution comprising water and a compound of formula (4),

where R², and R³, are independently as defined for the compound of formula (1);

R⁵ and R⁶ are independently selected from the definitions of R¹, R² and R³ of formula (1);

R⁴ is a divalent bridging group selected from a substituted or unsubstituted O₁ to C₈ alkylene group that is linear, branched or cyclic; a substituted or unsubstituted C₂ to C₈ alkenylene group that is linear, branched or cyclic; a substituted or unsubstituted —C_(n)Si_(m)— group where n and m are independently a number from 0 to 8 and n+m is a number from 1 to 8; a substituted or unsubstituted C₅ to C₈ arylene group optionally containing 1 to 8 {—Si(R¹⁰)₂—O—} units; a substituted or unsubstituted heteroarylene group having 4 to 8 atoms in the aromatic ring optionally containing 1 to 8 {—Si(R¹⁰)₂—O—} units; a —(Si(R¹⁰)₂—O)_(p)— chain in which “p” is from 1 to 8; a substituted or unsubstituted C₁ to C₈ alkylene-C₅ to C₈ arylene group optionally containing 1 to 8 {—Si(R¹⁰)₂—O—} units; a substituted or unsubstituted C₂ to C₈ alkenylene-C₅ to C₈ arylene group optionally containing 1 to 8 {—Si(R¹⁰)₂—O—} units; a substituted or unsubstituted C₁ to C₈ alkylene-heteroarylene group having 4 to 8 atoms in the aromatic ring optionally containing 1 to 8 {—Si(R¹⁰)₂—O—} units; a substituted or unsubstituted C₂ to C₈ alkenylene-heteroarylene group having 4 to 8 atoms in the aromatic ring optionally containing 1 to 8 {—Si(R¹⁰)₂—O—} units; R¹⁰ is a substituted or unsubstituted C₁ to C₈ alkyl, C₈ to C₈ aryl, heteroaryl having from 4 to 8 carbon atoms in the aromatic ring or C₁ to C₈ alkoxy moiety; and “a” is an integer. In some embodiments, compounds of formula (4) are water-soluble. Additives with large values of “a” are likely to be more effective in increasing the ionic strength when they are in their ionic forms but may suffer from poor solubility in water when they are in their non-ionic forms. For the avoidance of doubt, it is pointed out that when “a”>0, in a repeat unit —N(R⁵)—R⁴—, R⁴ and R⁵ may have a different definition from another such repeat unit.

In some embodiments, the additive is an oligomer or a polymer that contains one or more than one nitrogen atom(s) that is sufficiently basic to be protonated by carbonic acid in the repeating unit of the oligomer or polymer. In accordance with one embodiment, the nitrogen atoms are within the backbone of the polymer. The additive of formula (4) is a specific example of such a polymer in which the nitrogen atom(s) are within the backbone of the polymer. In alternative embodiments, the additive is an oligomer or polymer that contains one or more than one nitrogen atom(s) that is sufficiently basic to be protonated by carbonic acid in a pendant group that is part of the repeating unit, but that is not situated along the backbone of the oligomer or polymer. In some embodiments, some or all of the nitrogen atom(s) that are sufficiently basic to be protonated by carbonic acid are amidine groups. Such amidine groups may be part of the backbone of the oligomer or polymer or may be in pendant group s that are part of the repeating unit.

Example polymer additives having formulae (5a-g) are shown below. In these formulae, “n” refers to the number of repeat units containing at least one basic group and “m” refers to the number of repeat units containing no basic group. Additives with large values of “n” are likely to be more effective in increasing the ionic strength when they are in their ionic forms but may have poor solubility in water when they are in their non-ionic forms. It is not necessary that the backbone of the polymer be entirely made of carbon and hydrogen atoms; in some embodiments, the backbone may comprise other elements. For example, the polymer may have a polysiloxane backbone with amine-containing side groups, a polyether backbone with amine-containing side groups, or the backbone can itself comprise amine groups. In some embodiments, it is preferably to have a backbone or side groups that is reasonably hydrophilic or polar. Without wishing to be bound by theory, it is contemplated that a hydrophilic or polar backbone or side groups can help the charged form of the additive from precipitating.

R¹ can be substituted with a tertiary amine, which may itself be further substituted with a tertiary amine, as shown in the compound of formula (4). Such tertiary amine sites may be protonated when contacted with CO₂, CS₂ or COS in the presence of water. Thus, in certain embodiments the present invention provides an ionic solution comprising water and a salt of formula (4).

It will be apparent that when the polymer additive is in its ionized form, in order to balance the positive charges on the quaternary ammonium sites in the cation, a number of anions equivalent to the number of protonated basic sites should be present. For example, in the ionized form of the polymer additive of formula (4), there will be (a+1) ⁻E₃CH anionic counterions for each cation having (a+1) quaternary ammonium sites in the salt of formula (4). Alternatively, some of the ⁻E₃CH ions are replaced by anions of formula CE₃ ²⁻.

Each of R¹, R², and R³ in the compound of formula (1) can be substituted with a tertiary amine which may itself be further substituted with a tertiary amine. Such tertiary amine sites may be protonated when contacted with CO₂, CS₂ or COS in the presence of water. However, not all amine compounds having more than one amine site (i.e. polyamines) may be capable of protonation by the trigger at every amine site. Thus, amine compounds of formula (4) may not be protonated at every tertiary amine site when contacted with CO₂, COS or CS₂. Consequently, it should not be assumed that all basic sites must be protonated in order to effectively raise the ionic strength of the switchable water.

Furthermore, the pK_(aH) (i.e. the pK_(a) of the conjugate acid (i.e., ionic form)) of the amine compound of formula (1) should not be so high as to render the protonation irreversible. In particular, the ionic form of the additive should be capable of deprotonation through the action of the non-ionizing trigger (which is described below to be, for example, heating, bubbling with a flushing gas, or heating and bubbling with a flushing gas). For example, in some embodiments, the pK_(aH) is in a range of about 6 to about 14. In other embodiments, the pK_(aH) is in a range of about 7 to about 13. In certain embodiments the pK_(aH) is in a range of about 7.8 to about 10.5. In some embodiments, the pK_(aH) is in a range of about 8 to about 10.

Additives useful in a switchable water can have higher aliphatic (C₅-C₈) and/or siloxyl groups. Monocyclic, or bicyclic ring structures, can also be used. A higher number of aliphatic groups can cause a compound to be waxy and water-immiscible at room temperature. As described above, this may be advantageous if it means that the non-ionic form of the additive is water-immiscible, but the ionic form is water miscible.

In certain embodiments, the additive is liquid at room temperature.

It is preferred that the aliphatic and/or siloxyl chain length is 1 to 6, more preferably 1 to 4. A siloxyl group contains {—Si(R¹⁰)₂—O—} units; where R¹⁰ is a substituted or unsubstituted C₁ to C₈ alkyl, C₅ to C₈ aryl, heteroaryl having from 4 to 8 carbon atoms in the aromatic ring or C₁ to C₈ alkoxy moiety. Conveniently, in some discussions herein, the term “aliphatic/siloxyl” is used as shorthand to encompass aliphatic, siloxyl, and a chain which is a combination of aliphatic and siloxyl units.

Optionally the additive comprises a group that includes an ether or ester moiety. In preferred embodiments, an aliphatic group is alkyl. Aliphatic groups may be substituted with one or more moieties such as, for example, alkyl, alkenyl, alkynyl, aryl, aryl halide, hydroxyl, heteroaryl, non-aromatic rings, Si(alkyl)₃, Si(alkoxy)₃, halo, alkoxy, amino, ester, amide, amidine, guanidine, thioether, alkylcarbonate, phosphine, thioester, or a combination thereof. Reactive substituents such as alkyl halide, carboxylic acid, anhydride and acyl chloride are not preferred.

Strongly basic groups such as amidines and guanidines may not be preferred if their protonation by carbonic acid is difficult to reverse.

In other embodiments of the invention, substituents are lower aliphatic/siloxyl groups, and are preferably small and non-reactive. Examples of such groups include lower alkyl (C₁ to C₄) groups. Preferred examples of the lower aliphatic groups are CH₃, CH₂CH₃, CH(CH₃)₂, C(CH₃)₃, Si(CH₃)₃, CH₂CH₂OH, CH₂CH(OH)CH₃, and phenyl. Monocyclic, or bicyclic ring structures, may also be used.

It will be apparent that in some embodiments substituents R may be selected from a combination of lower and higher aliphatic groups. Furthermore, in certain embodiments, the total number of carbon and silicon atoms in all of the substituents R¹, R², R³ and R⁴ (including optional substituents) of a water-soluble compound of formula (1) may be in the range of 3 to 20, more preferably 3 to 15.

Referring to FIG. 1, a chemical scheme and schematic drawing are shown for a switchable ionic strength solvent system of a water-miscible amine additive of formula (1) and water. The chemical reaction equation shows an additive (non-ionic form) which is an amine compound of formula (1) and water on the left hand side and an ionic form of the additive as an ammonium bicarbonate salt of formula (3) on the right hand side. This reaction can be reversed, as indicated. The schematic shows the same reaction occurring in the presence of tetrahydrofuran (THF) wherein a single-phase aqueous solution of an amine additive (e.g., a compound of formula (1)) that is water-miscible, water and THF is shown on the left side under a blanket of N₂. A two phase (layered) mixture is shown on the right side under a blanket of CO₂. The two phases being an aqueous solution of the salt of formula (3) comprising ammonium bicarbonate and water, and THF.

Referring to FIG. 2, structures of a number of compounds of formula (1) are provided. DMEA or DMAE is N,N-(dimethylamino)ethanol, which in formula (1) has R¹ is methyl; R² is methyl; and R³ is C₂H₄OH). MDEA is N-methyl diethanolamine, which in formula (1) has R¹ is methyl; R² is C₂H₄OH; and R³ is C₂H₄OH). Both compounds, DMEA and MDEA, are monoamines having a single tertiary amine group. TMDAB is N,N,N′,N′-tetramethyl-1,4-diaminobutane, which in formula (1) has R¹ is methyl; R² is methyl; R³ is C₄H₈N(CH₃)₂). THEED is N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, which in formula (1) has R¹ is C₂H₄OH; R² is C₂H₄OH; and R³ is C₂H₄N(C₂H₄OH)₂). Compounds TMDAB and THEED are diamines having two tertiary amine groups. Compound DMAPAP is a triamine, having three tertiary amine groups, 1-[bis[3-(dimethylamino)]propyl]amino]-2-propanol, which in formula (1) has R¹ is methyl; R² is methyl; and R³ is C₃H₆N(CH₂CH(OH)CH₃)C₃H₆N(CH₃)₂). Compound HMTETA is a tetramine, having four tertiary amine groups, 1,1,4,7,10,10-hexamethyl triethylenetetramine, which in formula (1) has R¹ is methyl; R² is methyl; and R³ is C₂H₄N(CH₃)C₂H₄N(CH₃)C₂H₄N(CH₃)₂). These compounds are discussed further in the working examples.

Referring to FIG. 3, multiple ¹H NMR spectra are shown from a MDEA switchability study carried out in D₂O at 400 MHz. This is discussed in Example 4 below.

Referring to FIG. 4, multiple ¹H NMR spectra are shown from a DMAE switchability study carried out in D₂O at 400 MHz. This is discussed in Example 4 below.

Referring to FIG. 5, multiple ¹H NMR spectra are shown from a HMTETA switchability study carried out in D₂O at 400 MHz. This is discussed in Example 4 below.

Referring to FIG. 6, multiple ¹H NMR spectra are shown from a DMAPAP switchability study carried out in D₂O at 400 MHz. This is discussed in Example 4 below.

Referring to FIG. 7, conductivity spectra are shown for the responses to a CO₂ trigger over time the following solutions: 1:1 v/v H₂O:DMAE; 1:1 v/v H₂O:MDEA; and 1:1 w/w H₂O:THEED. Experimental details are discussed in Example 5 below.

Referring to FIG. 8, conductivity spectra are shown for the responses of 1:1 v/v H₂O:DMAE; 1:1 v/v H₂O:MDEA; and 1:1 w/w H₂O:THEED solutions, which had been switched with a CO₂ trigger, to the removal of CO₂ by nitrogen bubbling over time. Experimental details are discussed in Example 5 below.

Referring to FIG. 9, a plot of the degree of protonation of 0.5 M solutions of DMAE and MDEA in D₂O and a 0.1 M aqueous solution of THEED in D₂O resulting from exposure to a CO₂ trigger over time is shown. This is discussed in Example 6 below.

Referring to FIG. 10, a plot of the degree of deprotonation of 0.5 M solutions of DMAE and MDEA in D₂O and a 0.1 M solution of THEED in D₂O, which have been switched with a CO₂ trigger, to the removal of the trigger by nitrogen bubbling over time is shown. This is discussed in Example 6 below.

Referring to FIG. 11, conductivity spectra for the responses of 1:1 v/v H₂O: amine solutions to a CO₂ trigger over time, in which the amine is TMDAB (♦), HMTETA (▪), and DMAPAP (▴), is shown. This is discussed in Example 7 below.

Referring to FIG. 12, conductivity spectra for the responses of 1:1 v/v H₂O: amine solutions, which have been switched with a CO₂ trigger, to the removal of the trigger by nitrogen bubbling over time, in which the amine is TMDAB (♦), HMTETA (▪), and DMAPAP (▴), are shown. This is discussed in Example 7 below.

Referring to FIG. 13, five photographs A-E representing different stages of an experiment exhibiting how the switchable ionic strength character of amine additive TMDAB can be used to disrupt an emulsion of water and n-decanol are shown. This is discussed in Example 8 below.

In accordance with an alternative aspect, the switchable additive is an amidine having formula (6):

where R¹, R², and R³ are each, independently, as defined above. The ionized form of the additive of formula (6) is:

where n is a number from 1 to 6 sufficient to balance the overall charge of the amidinium cation, and E is O, S or a mixture of O and S.

Ionizing and Non-Ionizing Triggers

As used herein, a trigger is a change that leads to a chemical reaction or a series of chemical reactions. A trigger can either be an ionizing trigger, which acts to effect conversion of the additive to its ionic form (e.g., protonated), or a non-ionizing trigger, which acts to effect conversion of the additve to its non-ionic form (e.g., deprotonated).

As the skilled person will know, there are several ways to protonate a compound in the presence of water. Likewise, there are several ways to deprotonate a compound in the presence of water. In accordance with some embodiments, a non-reversible switch between a non-ionic (e.g., deprotonated amine) state and an ionic (protonated) state is sufficient. In accordance with other embodiments, a non-reversible switch between an ionic (e.g., protonated amine) state and a non-ionic (deprotonated) state is sufficient. In preferred embodiments the switching between ionic and non-ionic states is reversible. Accordingly the following discussion will describe several triggers.

An example of a non-ionizing trigger for converting the ionic state (e.g., protonated amine) to the non-ionic state (e.g., deprotonated amine) in an aqueous solution that has little or no dissolved CO₂, is addition of a base to the aqueous solution. An example of an ionizing trigger for converting the non-ionic state (e.g., deprotonated amine) to the ionic state (e.g., protonated amine) in an aqueous solution, is addition of an acid to the aqueous solution.

The compound of formula (1) can advantageously be converted, in the presence of water, from a water-soluble non-ionic amine form to an ionic form that is also water-soluble. The conversion occurs when the aqueous non-ionic solution is contacted with an ionizing trigger that is a gas that liberates hydrogen ions in the presence of water. Hydrogen ions protonate the amine nitrogen of the non-ionic compound to form a cation and, in the case of a CO₂ trigger, bicarbonate anion acts as a counterion and a salt form is formed. This aqueous salt solution is a single-phase ionic aqueous solution. More particularly, the ionic form is an ammonium salt. One skilled in the art will recognize that a small amount of carbonate anions will also form and may act as counterions to the protonated ammonium cations.

In the example in which the additive is immiscible or insoluble, or poorly miscible or poorly soluble, in water, it can be converted, in the presence of water, to an ionic form that is more water-soluble. For example the conversion can occur when the mixture of non-ionic additive and water is contacted with a trigger gas that liberates hydrogen ions in the presence of water. Hydrogen ions protonate the amine nitrogen of the non-ionic compound to form a cation and, in the case of a CO₂ trigger, bicarbonate anion acts as a counterion and a salt form is formed. This aqueous salt solution is a single-phase ionic aqueous solution. More particularly, the ionic form is an ammonium salt. One skilled in the art will recognize that a small amount of carbonate anions will also form and may act as counterions to the protonated ammonium cations.

As used herein, “gases that liberate hydrogen ions” fall into two groups. Group (i) includes gases that liberate hydrogen ions in the presence of a base, for example, HCN and HCl (water may be present, but is not required). Group (ii) includes gases that when dissolved in water react with water to liberate hydrogen ions, for example, CO₂, NO₂, SO₂, SO₃, CS₂ and COS. For example, CO₂ in water will produce HCO₃ ⁻ (bicarbonate ion) and CO₃ ²⁻ (carbonate ion) and hydrogen counterions, with bicarbonate rather than carbonate being the predominant anionic species at pH 7. One skilled in the art will recognize that the gases of group (ii) will liberate a smaller amount of hydrogen ions in water in the absence of a base, and will liberate a larger amount of hydrogen ions in water in the presence of a base.

Preferred gases that liberate hydrogen ions are those wherein the salt form switches to its non-ionic (amine) form when the same gas is expelled from the environment. CO₂ is particularly preferred. Hydrogen ions produced from dissolving CO₂ in water protonate the amine. In such solution, the counterion for the ammonium ion is predominantly bicarbonate. However, some carbonate ions may also be present in solution and the possibility that, for example, two ammonium molecules, each with a single positive charge, associate with a carbonate counterion is not excluded. When CO₂ is expelled from the solution, the ammonium cation is deprotonated and thus is converted to its non-ionic (amine) form.

Of group (ii) gases that liberate hydrogen ions, CS₂ and COS behave similarly to CO₂ such that their reaction with amine and water is fairly easily reversed. However, they are not typically preferred because their use in conjunction with water and an amine could cause the formation of highly toxic H₂S. In some embodiments of the invention, alternative gases that liberate hydrogen ions are used instead of CO₂, or in combination with CO₂, or in combination with each other. Alternative gases that liberate hydrogen ions (e.g., HCl, SO₂, HCN) are typically less preferred because of the added costs of supplying them and recapturing them, if recapturing is appropriate. However, in some applications one or more such alternative gases may be readily available and therefore add little to no extra cost. Many such gases, or the acids generated from their interaction with water, are likely to be so acidic that the reverse reaction, i.e., converting the ammonium salt to the amine form, may not proceed to completion as easily as the corresponding reaction with CO₂. Group (i) gases HCN and HCl are less preferred triggers because of their toxicity and because reversibility would likely require a strong base.

Contacting a water-soluble compound of formula (1) with a CO₂, CS₂ or COS trigger in the presence of water may preferably comprise: preparing a switchable water comprising water and a water-soluble additive of formula (1); and contacting the switchable water with a CO₂, CS₂ or COS trigger. Alternatively, the contacting a water-soluble compound of formula (1) with CO₂, CS₂ or COS in the presence of water may comprise: first preparing an aqueous solution of CO₂, CS₂ or COS in water; and subsequently mixing the aqueous solution with a water-soluble additive of formula (1) to form a switchable water. Alternatively, contacting a water-soluble additive of formula (1) with CO₂, CS₂ or COS in the presence of water may comprise: dissolving CO₂, CS₂ or COS in a water-soluble additive of formula (1) that is in a liquid state to provide a liquid; and mixing the non-aqueous liquid with water to form a switchable water.

Contacting a water-insoluble compound of formula (1) with a CO₂, CS₂ or COS trigger in the presence of water may preferably comprise: preparing a switchable water comprising water and a water-insoluble additive of formula (1); and contacting the switchable water with a CO₂, CS₂ or COS trigger. Alternatively, the contacting a water-insoluble compound of formula (1) with CO₂, CS₂ or COS in the presence of water may comprise: first preparing an aqueous solution of CO₂, CS₂ or COS in water; and subsequently mixing the aqueous solution with a water-insoluble additive of formula (1) to form a switchable water. Alternatively, the contacting a water-insoluble additive of formula (1) with CO₂, CS₂ or COS in the presence of water may comprise: dissolving CO₂, CS₂ or COS in a water-insoluble additive of formula (1) that is in a liquid state to provide a liquid; and mixing the non-aqueous liquid with water to form a switchable water.

Depletion of CO₂, CS₂ or COS from a switchable water is obtained by using a non-ionizing trigger such as: heating the switchable water; exposing the switchable water to air; exposing the switchable water to vacuum or partial vacuum; agitating the switchable water; exposing the switchable water to a gas or gases that has insufficient CO₂, CS₂ or COS content to convert the non-ionic state to the ionic state; flushing the switchable water with a gas or gases that has insufficient CO₂, CS₂ or COS content to convert the non-ionic state to the ionic state; or any combination thereof. A gas that liberates hydrogen ions may be expelled from a solution by simple heating or by passively contacting with a nonreactive gas (“flushing gas”) or with vacuum, in the presence or absence of heating. Alternatively and conveniently, a flushing gas may be employed by bubbling it through the solution to actively expel a gas that liberates hydrogen ions from a solution. This shifts the equilibrium from the ionic ammonium form to non-ionic amine. In certain situations, especially if speed is desired, both a flushing gas and heat can be employed in combination as a non-ionizing trigger.

Preferred flushing gases are N₂, air, air that has had its CO₂ component substantially removed, and argon. Less preferred flushing gases are those gases that are costly to supply and/or to recapture, where appropriate. However, in some applications one or more flushing gases may be readily available and therefore add little to no extra cost. In certain cases, flushing gases are less preferred because of their toxicity, e.g., carbon monoxide. Air is a particularly preferred choice as a flushing gas, where the CO₂ level of the air (today commonly 380 ppm) is sufficiently low that an ionic form (ammonium salt) is not maintained in its salt form. Untreated air is preferred because it is both inexpensive and environmentally sound. In some situations, however, it may be desirable to employ air that has had its CO₂ component substantially removed as a nonreactive (flushing) gas. By reducing the amount of CO₂ in the flushing gas, potentially less salt or amine may be employed. Alternatively, some environments may have air with a high CO₂ content, and such flushing gas would not achieve sufficient switching of ionic form to non-ionic amine form. Thus, it may be desirable to treat such air to remove enough of its CO₂ for use as a trigger.

CO₂ may be provided from any convenient source, for example, a vessel of compressed CO₂(g) or as a product of a non-interfering chemical reaction. The amines of the invention are able to react with CO₂ at 1 bar or less to trigger the switch to their ionic form.

It will be understood by the skilled person in the art that regeneration of a water-miscible compound of formula (1) from an ionic aqueous solution of a salt of formula (2) can be achieved by either active or passive means. The regeneration may be achieved passively if an insufficient concentration of an ionizing trigger, such as CO₂, is present in the surrounding environment to keep the additive switched to the ionic form. In this case, an ionizing trigger such as CO₂ could be gradually lost from the aqueous solution by natural release. No non-ionizing trigger, such as heating or active contacting with flushing gases would be required. Heating or contacting with flushing gases would be quicker but may be more expensive.

In studies described herein (see example 7), efficient contact between gas and solution was obtained using a fritted glass apparatus. Heat can be supplied from an external heat source, preheated nonreactive gas, exothermic dissolution of gas in the aqueous ionic solution, or an exothermic process or reaction occurring inside the liquid. In initial studies, the non-ionizing trigger used to expel CO₂ from solution and to switch from ionic form to amine was heat. However, CO₂ was expelled, and the salt was converted to the amine by contacting with a flushing gas, specifically, nitrogen. It is also expected that CO₂ can be expelled from the ionic solution merely by passively exposing the solution to air.

In some embodiments the amine additive in its non-ionic state is a liquid, in other embodiments the amine additive in its non-ionic state is a solid. Whether liquid or solid, they may be miscible or immiscible with water.

In some embodiments the ionic form of the additive (e.g., ammonium bicarbonate) is a liquid, in other embodiments the ionic form of the additive is a solid. Whether liquid or solid, they may be miscible or immiscible with water.

It is not significant whether neat ammonium bicarbonate salt is a solid or a liquid as long as it is water soluble such that a single phase solution is provided of the ionic aqueous solution. It will be apparent that at least a molar equivalent of water is required to react with the CO₂ to provide the carbonic acid to protonate a nitrogen site(s) of the amine group of the compound of formula (1) to form the ammonium cation.

In embodiments where a neat ammonium bicarbonate of formula (3) is a solid and not a liquid, more than a molar equivalent of water relative to the number of nitrogen sites should be present in the aqueous solution to ensure the complete dissolution of the salt in the ionic aqueous solution. In some embodiments, the amount of water is 1 or more weight equivalents relative to the compound of formula (1).

In some embodiments, the mole ratio of water and basic nitrogen sites in the amine capable of protonation is at least about equimolar. It will be apparent to one skilled in the art that when the ionic form is prepared from this mixture, there will remain little or no unreacted reactant(s), and thus little or no water after conversion to the salt form.

In other embodiments, the ratio of non-gaseous reactants is greater than equimolar, i.e., the number of moles of water is greater than the number of moles of basic nitrogen sites in the amine capable of protonation. This provides additional, unreacted water which is not consumed in the switching reaction. This may be necessary to ensure a single phase liquid mixture should the neat resulting salt be a solid, thereby providing a single phase aqueous solution. In some embodiments, a very high ratio of moles of water to moles of non-ionic additive (amine) is preferred so that the cost of the aqueous solvent can be decreased; it is assumed that the amine additive is more expensive than the water. It is preferred that sufficient water is present to dissolve the salt formed after switching so that an ionic aqueous solution is obtained.

If insufficient water is present to solubilize a solid ammonium bicarbonate formed after switching, unsolubilized salt will be present as a precipitate. For instance, should the ratio of {moles of water} to {moles of basic nitrogen sites in the amine capable of protonation} be equimolar, substantially all the water would be consumed in a complete switching reaction. If the salt was a solid rather than an ionic liquid, this solid would form as a precipitate. The formation of the salt as a precipitate may be advantageous in some circumstances because it is easily recoverable, for instance by filtration.

Systems and Methods Employing Switchable Water

As described briefly above, an aspect provided herein is a method and system for switching the ionic strength of water or an aqueous solution. The method comprises the step of mixing water or an aqueous solution with a switchable additive, before, after or simultaneously with the introduction of an ionizing trigger to ionize the switchable additive and consequently raise the ionic strength of the mixture of the water or the aqueous solution and the switchable additive. Optionally, the method additionally comprises the step of introducing a non-ionizing trigger to reverse the ionization of the switchable additive.

Also provided is a switchable water system that comprises: means for providing a switchable additive comprising at least one nitrogen that is sufficiently basic to be protonated by carbonic acid; means for adding the additive to water or to an aqueous solution to form an aqueous mixture with switchable ionic strength; means for exposing the water or aqueous solution to an ionizing trigger, such as CO₂, COS, CS₂ or a combination thereof, to raise the ionic strength of the aqueous mixture with switchable ionic strength; and, optionally, means for exposing the mixture with raised ionic strength to a non-ionizing trigger, such as (i) heat, (ii) a flushing gas, (iii) a vacuum or partial vacuum, (iv) agitation, (v) or any combination thereof, to reform the aqueous mixture with switchable ionic strength. As will be appreciated, the means for exposing the water or aqueous solution to the ionizing trigger, can be employed before, after or together with the means for adding the additive to the water or the aqueous solution.

FIG. 21 provides an example of a switchable water system as described above. In the system embodiment depicted in FIG. 21, the system includes means for contacting the non-ionized form of a switchable water with the ionizing trigger, which, in this example is CO₂. Following contact with the ionizing trigger, the switchable water is reversibly converted to its ionic form. As also depicted in FIG. 21, the system in this example further comprises a means for introducing a non-ionizing trigger to the ionized form of the switchable water. In this example, the non-ionizing trigger is air.

The following is a non-limiting list of applications of systems and methods employing switchable water:

-   -   1. In Osmosis (either by Forward Osmosis (FO) or by Forward         Osmosis followed by Reverse Osmosis (FO/RO))         -   a. For production of freshwater by desalination of seawater             or brackish water.         -   b. For partial dewatering of wastewater, process water, or             other industrial aqueous solutions (whether waste or in a             process). The osmosis concentrates the wastewater/process             water/industrial aqueous solution and produces a purified             water stream that can be directly recycled or disposed of,             or further purified or processed for recycling or disposal.     -   2. In Forcing Immiscibility         -   a. For the drying of (i.e., removal of water from) organic             liquids by forcing the water-content in the organic liquid             to form a second liquid phase.         -   b. For the recovery of organic liquids from water by forcing             the organic content in the water to form a second liquid             phase.         -   c. For forcing two immiscible aqueous phases to form (for             separating water-soluble polymers such as polyethylene             glycol (PEG) from salts or for concentrating solutions of             water-soluble polymers such as PEG).     -   3. In Forcing Insolubility         -   a. For recovering a solid compound or compounds (such as an             organic product, e.g., an active pharmaceutical ingredient             (API) or a contaminant) from water or from an aqueous             mixture. The recovered solid compound or compounds can be             the target compound or compounds or an undesired compound or             compounds (such as contaminants or by-products). This can be             useful, for example, after an organic synthesis in water;             after the extraction of an organic into water; for             recovering proteins from water; for decontaminating             contaminated water; for causing a coating, dye or mordant to             come out of aqueous solution and attach itself onto a solid.         -   b. For adjusting the solubility of salts in water (i.e., the             solubility of the salt would be different in the ionic             switchable water than in the non-ionic switchable water).             Possibly useful in mining or in separations involving salts.         -   c. For adjusting the partition coefficient of solutes             between an aqueous phase and an organic liquid phase.             Certain systems and methods employing switchable water are             useful in catalysis, extractions, washing of products,             separations of mixtures, etc.     -   4. In Breaking Dispersions         -   a. For breaking emulsions. Can be useful, for example, in             the oil industry during or after enhanced oil recovery,             during or after pipelining of heavy crudes or bitumen,             during or after wastewater treatment, in the treatment of             rag layers.         -   b. For breaking suspensions. Can be useful, for example, in             removal of suspended solids/particles from water (e.g.,             wastewater or storm water). For example, the present methods             and systems can be used in oil sands processing and tailings             ponds, in mining, in the treatment of wastewater from             mining, in minerals processing and separation, in treatment             of wastewater from other industries, in latex preparation,             handling and precipitation, in             emulsion/microemulsion/miniemulsion/suspension             polymerization. In a specific example, the methods and             systems can be used in removal of fine clay particles from             water.         -   c. For breaking foams and froths. Can be useful, for             example, in the oil industry for suppressing foams, in             mineral separations, in the treatment of aqueous streams             after mineral separations.     -   5. In Causing Other Properties of Aqueous Solutions to Change         -   a. For modifying density. The density of the ionic form of a             switchable water is expected to be different from the             density of the non-ionic version. This density change can be             useful in the separation of solid materials like polymers             because some would float and some would sink at each density             and modifying the density could allow the separation of             different polymers at different densities.         -   b. For modifying conductivity, for example, in sensors,             liquid switches.         -   c. For modifying viscosity. The viscosity of the ionic form             of a switchable water solution is different from the             non-ionic version.

In specific embodiments, this system and method are used, for example:

-   -   to remove water from a hydrophobic liquid or a solvent;     -   to remove water from a hydrophilic organic liquid such as an         alcohol;     -   to remove or isolate a solute from an aqueous solution;     -   to remove or isolate a hydrophobic liquid or solvent from an         aqueous mixture;     -   to remove salt and/or generate fresh water in a desalination         process;     -   to destabilize or disrupt micelles and/or to deactivate a         surfactant;     -   to provide a switchable antifreeze, a switchable electrolyte         solution, a switchable conducting solution, or an electrical         switch; or     -   to provide a CO₂, COS, CS₂ sensor.

In one embodiment, there is provided a method of extracting a selected substance from a starting material(s) that comprises the selected substance. In some embodiments, the selected substance is soluble in an aqueous solution comprising the non-ionic form of a swichable water (comprising the a non-ionic form of the switchable additive) with zero or low ionic strength, and the selected substance is insoluble in an aqueous solution comprising the ionic form of a switchable water (comprising the ionized form of the additive), which has a higher ionic strength. For instance, the starting material may be a solid impregnated with the selected substance. For another instance, the starting material may be a liquid mixture of the selected substance and a hydrophobic liquid. This method of extracting a selected substance is particularly effective if the selected substance is soluble in the non-ionic aqueous solution. The selected substance, which may be a liquid or a solid, dissolves in the non-ionic aqueous solution comprising an additive of formula (1) and can thereby be readily separable from any water-insoluble remaining starting material (e.g., by filtration) and can be separated from the hydrophobic liquid (e.g., by decantation). Once the non-ionic aqueous solution comprising the selected compound is isolated, the selected substance can be separated from the aqueous phase (i.e., “salted out”) by converting the non-ionic aqueous solution to an ionic aqueous solution. The selected substance will then separate out and can be isolated.

Using methods and systems described herein it is possible to separate certain water-soluble selected compounds from an aqueous solution. Once the selected compounds are dissolved in an aqueous solution, and optionally separated from other non-soluble compounds by, for example, filtration, the selected compounds can be isolated from the aqueous solution without having to input a large amount of energy to boil off the water. Conveniently, this separation is done by increasing the ionic strength (amount of charged species) in the aqueous solution (more commonly referred to as “salting out”) resulting in a separation of the selected compound from the distinct aqueous phase. The selected compound can then be isolated from the aqueous solution be decanting it or filtering it, as appropriate. Thus, an aqueous solution whose ionic strength is altered upon contact with a suitable trigger can dissolve or separate from a selected compound in a controlled manner. Importantly, this method of salting out is readily reversible, unlike the conventional method of salting out (e.g., adding NaCl to water). A system for employing such a method includes, in addition to the components set out above, means for mechanical separation of solids from a liquid mixture.

In an embodiment, the invention provides a method of removing water (i.e., drying) from hydrophobic liquids such as solvents. As described in detail herein, additives form a salt in the presence of water and CO₂, COS or CS₂. Accordingly, additives added to wet solvent and an ionizing trigger gas (in any combination) cause any water that was in the wet solvent to separate out as a distinct ionic component in an aqueous phase. A system for employing such a method includes, in addition to the components set out above, means for extracting a water immiscible liquid phase from an aqueous solution.

A conceptual model of such a system is shown in FIG. 1, which shows the reversible separation of tetrahydrofuran (THF) from an aqueous solution of a compound of formula (1). This figure shows that when THF is mixed with a non-ionic aqueous solution, THF is miscible with the non-ionic aqueous solution, providing a single phase. As discussed in working examples 1 and 2, THF was experimentally shown to be miscible with the non-ionic aqueous solution. Further, THF was isolated from the mixture by switching the additive in the solvent from its non-ionic form to its ionic form (ammonium bicarbonate) in order to increase the ionic strength and force THF from the aqueous solution.

Specifically, as discussed in working examples 1 and 2, the aqueous solution was contacted with CO₂ to switch the amine to its ammonium bicarbonate form (ionic form) as shown by formula (3). The contacting was carried out by treating a miscible mixture of THF, water and water-soluble amine compound of formula (1) with carbonated water or actively exposing the mixture to CO₂. The THF then formed a non-aqueous layer and the ammonium bicarbonate remained in an increased ionic strength aqueous layer (“water+salt (3)”). The non-aqueous and aqueous layers are immiscible and formed two distinct phases, which can then be separated by decantation, for example. Once separated, the non-aqueous and aqueous layers provide an isolated non-aqueous phase comprising THF and an isolated aqueous phase comprising the ammonium bicarbonate form of additive in the switchable solvent. In this way, the solvent is separated from the THF without distillation. While it is unlikely that every single molecule of THF will be forced out of the aqueous phase, a majority of the THF can be forced out by this method. The amount of THF that remains in the aqueous phase will depend on several factors, including nature and concentration of additive, temperature, effect of other species in solution, amount of CO₂ (or other gas(ses) that releases protons in water) in the water, and the number of basic sites on the additive that are protonable by carbonic acid.

The ammonium bicarbonate salt of formula (3) in the aqueous phase was switched back to its non-ionic form. The aqueous solution of salt (3) which has been switched back to a non-ionic aqueous solution can then be used to dissolve or extract further THF.

Note that the ability of the liquid mixture of water and amine additive (e.g., compound of formula (1)) to dissolve a selected compound may be greater than the ability of pure water to dissolve the same selected compound because the additive may help the desired compound to dissolve in the aqueous solution. This may be because of a polarity-lowering effect of the amine, because of preferential solvation of the molecules of the desired compound by the molecules of the amine additive, and/or because of a miscibility-bridging effect in which the addition of a compound of intermediate polarity increases the mutual miscibility between a low-polarity liquid and a high-polarity liquid.

When the aqueous solutions with switchable ionic strength are switched between their lower ionic strength state and their higher ionic strength state, characteristic of the solution are changed. Such characteristics include: conductivity, melting point, boiling point, ability to solubilise certain solutes, ability to solubilise gases, osmotic pressure, and there may also be a change in vapour pressure. As discussed herein, the switchable ionic strength also affects surfactants by changing their critical micelle concentration and by affecting their ability to stabilize dispersions. Variation of such characteristics can be used, for example, the reversibly switchable ionic strength solution can be a reversibly switchable antifreeze, a reversibly switchable electrolyte solution, or a reversibly switchable conducting solution.

A further aspect provides a non-ionic switchable water mixture that is largely nonconductive (or only weakly conductive) of electricity, that becomes more conductive when it is converted to its ionic form, and that this change is reversible. Such a conductivity difference would enable the mixture to serve as an electrical switch, as a switchable medium, as a detector of CO₂, COS or CS₂, or as a sensor of the presence of CO₂, COS or CS₂. This ability of the ionic liquid to conduct electricity can have applications in electrochemistry, in liquid switches and in sensors and/or detectors. Common, affordable CO₂ sensors are typically effective at 2-5% CO₂. CO₂ sensors that work between 2-100% are usually large and prohibitively expensive. A chemical approach based on switchable ionic strength solutions can cost much less.

Further provided is a method for maintaining or disrupting miscibility of two liquids where the first liquid is miscible with low ionic strength water but is immiscible with higher ionic strength water and the second liquid is the reversible switchable ionic strength aqueous solvent described herein. In a mixture of the first and second liquids, they are miscible when the switchable solvent is in its non-ionic form. To disrupt the miscibility, a trigger is applied, causing the ionic strength of the switchable solvent to increase and the newly-immiscible liquids to separate. Alternatively, the first liquid may be a liquid that is miscible with aqueous solutions of high ionic strength and immiscible with aqueous solutions of low ionic strength. In such a case the ionic and non-ionic forms of the switchable solvent should be used to maintain and disrupt the miscibility, respectively.

Another aspect is a method for “salting-in” of solutes that are more soluble in water of high ionic strength than in water of low ionic strength. For example, an aqueous solution of switchable additive at high ionic strength is used as a solvent for a solute, and the switching of the solution to low ionic strength causes the solute to form a second phase or precipitate or to partition into an existing second phase.

Another aspect provides a method of deactivating surfactants. Surfactants (also known as detergents and soap) stabilize the interface between hydrophobic and hydrophilic components. In aqueous solutions, detergents act to clean oily surfaces and clothing by making the (hydrophobic) oil more soluble in water (hydrophilic) by its action at the oil-water interface. Once a cleaning job is finished, soapy water with hydrophobic contaminants remains. To recover the oil from the soapy water, salt can be added to the water and most of the oil will separate from the salt water. With the switchable ionic strength aqueous solution of the present invention, after a cleaning job, the oil can be recovered from the soapy water solution merely by applying a trigger to reversibly increase the solutions ionic strength. The trigger causes the ionic strength to increase, thereby deactivating the surfactant. Many surfactants are unable to function properly (effectively stabilize dispersions) at conditions of high ionic strength. The oil then separates from the aqueous phase, and can be decanted off. Then the aqueous solution can be triggered to decrease the ionic strength. Regenerated soapy water can then be reused, over and over.

Another aspect provides switchable water of switchable ionic strengths that are used to stabilize and destabilize emulsions, which may include surfactant-stabilized emulsions. Emulsions of oil and water that include surfactants are used in oil industries to control viscosity and enable transport of oil (as an emulsion) by pipeline. Once the emulsion has been transported, however, it is desirable to separate the surfactant-supported emulsion and recover oil that is substantially water-free. In its non-ionized form, amine additive does not significantly interfere in the stability of an emulsion of water and a water-immiscible liquid (e.g., hexane, crude oil). However, once switched to its ionic form, the increased ionic strength of the solution interferes with the stability of the emulsion, resulting in a breaking of the emulsion. In surfactant-stabilized emulsions, the higher ionic strength solution may interfere with the surfactant's ability to stabilize the emulsion. This reversible switch from lower to higher ionic strength is preferable over destabilizing emulsions by traditional means (i.e., increasing the ionic strength by adding of a traditional salt such as NaCl). This preference is because the increase in ionic strength caused by the addition of a traditional salt is difficult to reverse without a large input of energy.

Creating an emulsion is possible, for example by adding a water-immiscible liquid to the lower ionic strength switchable aqueous solution as described previously, to form two phases. Then, a surfactant that is soluble in the aqueous phase should be added to a concentration above the critical micelle concentration of the surfactant. Shear or mixing of the mixture then creates an emulsion. As discussed above, the resultant emulsion can be destabilized by treatment with an ionizing trigger, such as by bubbling it with CO₂, COS or CS₂ to raise the ionic strength of the aqueous phase. Subsequent removal of CO₂, COS or CS₂ by treatment with a non-ionizing trigger, such as by bubbling the mixture with a flushing gas and/or by heating it lowers the ionic strength allowing the system to return to the initial conditions.

Non-limiting examples of emulsions include mixtures of water with: crude oil; crude oil components (e.g., gasoline, kerosene, bitumen, tar, asphalt, coal-derived liquids); oil (including oil derived from pyrolysis of coal, bitumen, lignin, cellulose, plastic, rubber, tires, or garbage); vegetable oils; seed oils; nut oils; linseed oil; tung oil; castor oil; canola oil; sunflower oil; safflower oil; peanut oil; palm oil; coconut oil; rice bran oil; fish oils; animal oils; tallow; or suet. Other non-limiting examples of emulsions include water with colloidal particles, colloidal catalysts, colloidal pigments, clay, sand, minerals, soil, coal fines, ash, mica, latexes, paints, nanoparticles including metallic nanoparticles, nanotubes.

Another aspect provides aqueous solutions of switchable ionic strength, or switchable water, which are used to stabilize and destabilize reverse emulsions.

A suspension is a finely divided solid that is dispersed but not dissolved in a liquid. In an aspect of the invention, aqueous solutions of switchable ionic strength are used to stabilize and destabilize suspension of solids in water, which may include surfactant-stabilized suspensions. In its non-ionized form, amine additive does not interfere in the stability of a suspension. However, once the additive is switched to its ionic form, the increased ionic strength may significantly destabilize a suspension and/or it may inhibit the ability of a surfactant to stabilize such a suspension, resulting in coagulation of the solid particles. This reversible switch from lower to higher ionic strength is preferable to destabilizing a suspension by adding traditional salts (e.g., NaCl) because the increase in ionic strength caused by the addition of a traditional salt is difficult to reverse without a large input of energy. Typical examples of such suspensions may include polymers (e.g., polystyrene), clays, minerals, tailings, colloidal dyes, and nanoparticles including metallic nanoparticles. Increasing the ionic strength of the solution by applying a trigger, causes small solid particles to aggregate or coagulate to form larger particles that settle to the bottom of the solution. Application of a trigger to convert from higher ionic strength to lower ionic strength (e.g., removal of CO₂) allows for redispersion of the particles, regenerating the suspension.

In an alternative aspect there is provided, aqueous solutions comprising switchable water of switchable ionic strength that are used to stabilize and destabilize foam (i.e., gas-in-liquid), which may include surfactant-stabilized foams. In its non-ionized form, the switchable additive does not interfere in the stability of a foam. However, once the additive is switched to its ionic form, the increased ionic strength interferes with the stability of the foam and/or inhibits a surfactant's ability to stabilize a foam, resulting in the breaking of the foam. This reversible switch from lower to higher ionic strength is preferable to destabilizing foams by adding a traditional salt (e.g., NaCl) because the increase in ionic strength caused by the addition of a traditional salt is difficult to reverse without a large input of energy.

A gas in liquid emulsion can exist in the lower ionic strength aqueous solution that includes an amine additive. When a trigger is applied to increase the solution's ionic strength the foam is destabilized. The application of a trigger to convert it from the higher ionic strength solution to the lower ionic strength solution leads a newly generated foam to be stabilized in the solution. In this situation, a non-ionizing trigger to release CO₂, COS or CS₂ would preferably be application of a flushing gas (e.g., N₂, air). In an embodiment of the method of separating a solute from an aqueous solution, instead of separating the solute in a neat form, it is possible to add a water immiscible liquid (e.g., n-octanol) to the mixture. In the lower ionic strength form, the solute has a given partitioning between the aqueous phase and the hydrophobic phase. With application of a trigger, the aqueous phase converts to a higher ionic strength solution, which causes more of the solute to partition into the hydrophobic phase. In this embodiment, rather than the solute forming its own phase, the solute is dissolved in the hydrophobic phase. If desired, another trigger (e.g., removal of CO₂) lowers the ionic strength allowing the solute to return to the aqueous phase. A system for employing such a method would include, in addition to the components described above, means for providing the water immiscible liquid and means for extracting a water immiscible liquid phase from an aqueous solution

In another aspect there is provided, aqueous solutions of switchable ionic strength that are used to create aqueous/aqueous biphasic systems. A lower ionic strength aqueous solution with amine additive and a water-soluble polymer (e.g., poly(ethylene glycol) exists as a single phase. With application of a trigger, the aqueous phase converts to a higher ionic strength solution, which causes the mixture to form two separate phases. Specifically, the phases are the polymer and water that it carries with it since is quite water soluble and the aqueous solution of higher ionic strength. If desired, another trigger (e.g., removal of CO₂) lowers the ionic strength causing the system to recombine into a single aqueous phase.

In an embodiment of this aspect, there are two solutes in the aqueous solution of switchable ionic strength that comprises a water-soluble polymer (e.g., poly(ethylene glycol). The two solutes may be, for example, two different proteins. Each protein will separate from higher ionic strength aqueous solution (i.e., “salt out”) at a distinct and specific ionic strength. If a trigger increases the ionic strength of the switchable solution such that only one of the two proteins separates from the higher ionic strength aqueous phase, the one protein will partition into the water and water-soluble-polymer layer so that it is separated from the other protein. As described above, with another trigger to reduce the ionic strength, the aqueous solution can be used over and over again. In another embodiment of this aspect, a solute may partition from the higher ionic strength aqueous solution into the water with water-soluble-polymer layer in the form of a solid.

Another aspect of the invention is a method of drying hydrophobic liquids by separating the hydrophobic liquid from its water contaminant. As described herein, this separation is effected by adding an additive that forms a salt in the presence of water and CO₂, COS or CS₂. The salt can then be isolated from the hydrophobic liquid thereby removing its water contaminant. Non-limiting examples of hydrophobic liquids include solvents, alcohols, mineral oils, vegetable oils, fish oils, seed oils. In some embodiments of the invention the liquid that needs to be similarly dried is a hydrophilic liquid such as a smaller alcohol.

Yet another aspect of the invention provides a method of reversibly lowering an aqueous solution's boiling point. Another aspect of the invention provides a method of reversibly increasing an aqueous solution's boiling point.

Another aspect of the invention provides a method and system for altering the viscosity of an aqueous solution or mixture. It has been found that the use of switchable water to alter the ionic strength of an aqueous solution also results in an alteration in the viscosity of the aqueous solution. In one embodiment, the method and system for switching the viscosity of an aqueous system facilitates a reversible small change in viscosity. Such a method and system makes use of lower molecular weight switchable water additives. The dissolution in water of a lower molecular weight switchable water additive, in its non-ionic form, will generate a modest increase in viscosity over water alone. However, it has been found that addition of CO₂ to such a system still causes a decrease in viscosity making it valuable in those situations that require only small changes in viscosity.

In another embodiment, the method and system for switching the viscosity of an aqueous solution facilitates a relatively large reversible change in viscosity. Such a method and system makes use of higher molecular weight switchable water additives. The dissolution in water of a higher molecular weight switchable water additive, in its non-ionic form, will generate a significant increase in viscosity over water alone. As will be appreciated by a worker skilled in the art, the large molecular weight switchable water additive must be sufficiently soluble in water, when the additive is in its non-ionic form, to generate the large increase in viscosity over water alone. When a suitable ionizing trigger is introduced, the ionic form of the high molecular weight switchable water additive is generated, leading to a relatively large decrease in the viscosity of the solution.

A system and method for reversible alteration of viscosity would be useful, for example, in point to point transport of an otherwise viscous material in which its application calls for a higher viscosity, such as in conventional waterflooding techniques. Conventional waterflooding techniques are used for enhanced oil and gas recovery operations. Low viscosity, ionic form, polymer solutions could be injected into oil and gas wells at pressures lower than conventional polymer additives, at which point the solutions could be switched to a higher viscosity by use of a suitable trigger, which may help promote oil flow towards collection points. Once operations are complete it may be possible to lower the viscosity of the solution by switching on the polymer additive to it's ionic form, at which point the ionic form of the polymer additive solution could be pumped out of the well.

Another aspect of the invention provides a method and system for reversibly lowering an aqueous solution's boiling point. Another aspect of the invention provides a method of reversibly increasing an aqueous solution's boiling point.

An aspect of the invention provides a reversibly switchable antifreeze.

An aspect of the invention provides a reversibly switchable electrolyte.

An aspect of the invention is a method for reversibly controlling the attractive and repulsive forces existing in a multiphase mixture such as oil sands (also known as tar sands or bituminous sands). For example, in some embodiments, the high ionic strength aqueous solution of switchable additive could make some or all of the interactions between components become attractive, while some or all of the interactions would be less attractive or even be repulsive in the presence of low-ionic strength aqueous solution. Repulsive forces, for example between clay and bitumen, between clay particle and another clay particle, or between clay and sand particles, are acceptable or even desired in the separation of oil sands into bitumen and tailings, while, in contrast, repulsive forces are acceptable or even desired in the treatment and settling of tailings.

In preferred embodiments, conversion of the compound of formula (1) to the salt is complete. In certain embodiments, the conversion to salt is not complete; however, a sufficient amount of the amine is converted to the salt form to change the ionic strength of the liquid. Analogously, in some embodiments, the conversion of ionic form back to the amine compound of formula (1) that is water-miscible may not be complete; however a sufficient amount of the salt is converted to the amine compound of formula (1) that is water-miscible to lower the ionic strength of the solution.

An advantage of switchable water described herein is that it can facilitate syntheses and separations by eliminating the need to remove and replace water or an aqueous solution after each reaction step. With triggers that are capable of causing a drastic change in the ionic strength of the water or aqueous solution while it is still in the reaction vessel, it may be possible to use the same water or aqueous solution for several consecutive reaction or separation steps. This would eliminate the need to remove and replace the solvent water or aqueous solution. For example, a chemical reaction that requires an aqueous solvent could be performed using the switchable water while in its amine form as the solvent. Once the reaction is complete, the solvent could be switched to its higher ionic strength form which is substantially incapable of dissolving a product and/or side-product of the reaction. This would force the product to precipitate, if solid, or become immiscible, if liquid. The solvent could then be separated from the product by physical means such as, for example, filtration or decantation. The solvent could then be switched back to its lower ionic strength form by switching the ionic form to the water-miscible amine and reused. This method allows the use of an aqueous solvent without the requirement for an energy-intensive distillation step to remove the solvent. Such distillation steps may be complex because both the solvent and the product may have similar boiling points.

Reuse and recycling of solvents of the invention provide both economic and environmental benefits. The time required to switch between the higher and lower ionic strength solvents is short as demonstrated by studies described in Examples 6 and 7. In Example 6, an incomplete switch between an additive in ionic form and nonionic form can occur in 300 minutes with heating. Example 6 also shows that in excess of about 90% of the ionic forms of MDEA and THEED were converted back to their non-ionic forms. THEED was 98% deprotonated after 120 minutes of heating (75° C.) and bubbling with N₂ using a single needle. As shown in FIG. 12 and described in Example 7, conductivity of TMDAB was reduced approximately 95% in 90 minutes when heated at 80° C. and N₂ was bubbled through a glass frit. This result demonstrated a dramatic ionic strength reduction.

It is advantageous to convert from non-ionic amine form to ionic form and then back again (or vice-versa). The solvent comprising water and the additive in its amine form could be miscible with another liquid, and then the solvent could be switched to increased ionic strength form to allow for separation of the resulting two liquid components. The liquid components may or may not appear as distinct layers. Methods for separation of the components may include decanting, or centrifuging followed by decanting. After separation, it is desirable to convert an ionic form of the additive back to its non-ionic amine form in water. Thus the solvent can be reused.

In accordance with a specific embodiment, there is provided a system, as depicted in FIG. 22, for isolating or purifying one or more compounds from a mixture. The system includes a means, 10 (denoted in FIG. 22), for introducing a non-ionic switchable water to a mixture of compounds. In this example, the first compound is miscible in the non-ionic form of switchable water and the second compound is insoluble. Accordingly, the system additionally comprises means, 20 (denoted in FIG. 22), for mechanically collecting the second compound that is insoluble in the non-ionic switchable water. For example, the system can include means for collecting or removing the second compound by filtration thereby leaving a mixture, 30 (denoted in FIG. 22), that includes the non-ionic switchable water and the first compound. The system depicted in FIG. 22 further comprises means for contacting mixture, 30 (denoted in FIG. 22), with an ionizing trigger (e.g., CO₂) to increase the ionic strength of the switchable water and generate a two-phase mixture, 40 (denoted in FIG. 22), in which the first compound is no longer miscible with the switchable water. The system shown in FIG. 22 additionally comprises means, 50 (denoted in FIG. 22), for collecting the immiscible first compound. For example, the system can include means for decanting or otherwise collecting the top layer of mixture, 40 (denoted in FIG. 22), which top layer includes the first compound. Optionally, this system further includes means for reversing the ionic strength increase of the switchable water by introducing a non-ionizing trigger, such as air, to reform the non-ionic form of the switchable water, 60 (denoted in FIG. 22).

Switchable water can also be useful in water/solvent separations in biphasic chemical reactions. Separation of a liquid from a switchable solvent can be effected by switching the switchable solvent to its higher ionic strength form. This ability to separate solvents may be useful in many industrial processes where, upon completion of a reaction, the solvent can be switched to its higher ionic strength form with the addition of a trigger allowing for facile separation of the two distinct phases. Thus a switchable ionic strength solvent may be used in its lower ionic strength form as a medium for a chemical reaction. Upon completion of the reaction, the chemical product is readily separated from solution by switching the solvent to its higher ionic strength form. The switchable water solvent can then be recovered and reused.

To gain a better understanding of the invention described herein, the following examples are set forth. It should be understood that these examples are for illustrative purposes only. Therefore, they should not limit the scope of this invention in any way.

In the following Working Examples, a variety of tertiary amines have been studied for their properties as switchable additives in switchable ionic strength aqueous solutions (i.e., switchable water).

Results presented in the working examples, figures and tables show that six tertiary amines, selected from monoamines, diamines, triamines, tetraamines exhibited reversible switching ionic strength behavior. All of these compounds were miscible with water in aqueous solution, and in the presence of CO₂ switched to ammonium bicarbonate salt forms which were soluble in the aqueous phase. In addition, the working examples, figures and tables show polyamines that were successfully used to reversibly switch ionic strength behavior of aqueous systems.

Variations to the structure of these amine compounds are well within the skill of the person of ordinary skill in the art pertaining to the invention. These include minor substitutions, varying the length of a hydrocarbon chain, and the like.

As described in the working examples, several salts of formulae (2) and (3), and of polyamines have been formed according to the invention by reacting CO₂ with aqueous solutions of water-miscible amine compounds of formulae (1) and (4). The water system advantageously provides a rapid rate of reaction to form the ammonium bicarbonate compounds from the water-miscible compounds of formulae (1) and (4), and allows the dissolution of the ammonium bicarbonate compounds should they be solid at the temperature of the separation.

WORKING EXAMPLES

The following chemicals were used as received: ethanolamine, 2-(methylannino) ethanol, chloroform-d (99.8+ atom % d), D₂O (99.9+ atom % d), acetonitrile-d₃ (99.8+ atom % d), methanol-d₄ (99.8+ atom % d), 1,4-dioxane (99+%), DMAE, MDEA, TMDAB, THEED, DMAPAP and HMTETA (Sigma-Aldrich of Oakville, Ontario, Canada, or TCI of Portland, Oreg., USA); THF (99+%) and ethyl acetate (99.5+%) (Calcdon Laboratories, Ontario, Canada); hydrochloric acid (˜12 M, Fischer Scientific, Ottawa, Ontario, Canada); and DMSO-d₆ (99.9+ atom % d) Cambridge Isotope Labs, St Leonard, Canada).

Diethyl ether was purified using a double-column solvent purification system (Innovative Technologies Incorporated, Newbury Port, USA). Compressed gasses were from Praxair (Mississauga, Ontario, Canada): 4.0 grade CO₂ (99.99%), 5.0 grade Ar (99.999%), supercritical grade CO₂ (99.999%, H₂O<0.5 ppm), nitrogen (99.998%, H₂O<3 ppm) and argon (99.998%, H₂O<5 ppm).

Unless otherwise specified, water used in studies described herein was municipal tap water from Kingston, Ontario, Canada that was deionized by reverse osmosis and then piped through a MilliQ Synthesis A10 apparatus (Millipore SAS, Molsheim, France) for further purification.

DBU (Aldrich, Oakville, Ontario, Canada, 98% grade) was dried by refluxing over CaH₂ and distilled under reduced pressure onto 4 Å molecular sieves and then deoxygenated by repeated freeze/vacuum/thaw cycles or by bubbling with CO₂ followed by filtration to remove any bicarbonate precipitate.

¹H NMR and ¹³C NMR spectra were collected at 300 K on a Bruker AV-400 spectrometer at 400.3 and 100.7 MHz, respectively.

Comparative Example 1: Amidine and Water System

A bicyclic amidine DBU (1,8-diazabicyclo-[5.4.0]-undec-7-ene), having the following structure, was investigated as an additive to provide switchable ionic strength aqueous solutions.

DBU in non-ionic amidine form was soluble in water to provide a single phase aqueous solution. It was found to be capable of switching to a water-soluble amidinium bicarbonate salt form in the presence of water and a CO₂ trigger.

Initial experiments with a solution of DBU in water confirmed that compounds THF and 1,4-dioxane were miscible with the aqueous solution of DBU (non-ionic form) in the absence of CO₂, and were immiscible with the aqueous solution in the presence of CO₂ in which the amidine had been switched into its amidinium bicarbonate ionic form. However, it was found that it was not possible to liberate CO₂ from the ionic solution with moderate heating. The two-phase mixture of non-aqueous THF and aqueous amidinium bicarbonate that had been generated from exposure to CO₂ could not be converted to a single-phase aqueous solution of DBU (non-ionic form) and THF.

Specifically, a 1:1:1 (v/v/v) mixture of DBU, water and compound was added to a six dram vial containing a magnetic stirrer and fitted with a rubber septa. To introduce gas to the solution, a single narrow gauge steel needle was inserted and gas was bubbled through. A second narrow gauge steel needle was inserted to allow venting of the gaseous phase.

When the compound was THF, a single phase miscible liquid mixture was observed. After CO₂ was bubbled through the solution for 15 min, the mixture separated into two phases, an aqueous phase comprising a solution of the amidinium bicarbonate salt of DBU and a non-aqueous phase comprising THF. Bubbling N₂ through the mixture for several hours at 50° C. failed to cause the phases to recombine.

Similarly, a 1:1:1 (v/v/v) mixture of DBU, water and 1,4-dioxane was observed to be a single phase miscible liquid mixture. After CO₂ was bubbled through the solution for 60 min, the mixture separated into two phases, an aqueous phase comprising a solution of the amidinium bicarbonate salt of DBU and a non-aqueous phase comprising 1,4-dioxane. Bubbling N₂ through the mixture for several hours at 50° C. failed to cause the phases to recombine.

Thus, although an aqueous solution of the amidine DBU can be switched from a lower ionic strength form to a higher ionic strength form in order to force out THF or 1,4-dioxane from the solution, the switching was not found to be reversible at the given experimental conditions. It is likely that with high energy input such as high temperatures, reversible switching would be possible.

Comparative Example 2: Primary and Secondary Amine and Water Systems

A primary amine, ethanolamine, and a secondary amine, 2-(methylamino) ethanol were investigated as additives to provide switchable ionic strength aqueous solutions. Six dram vials comprising 3:3:1 (v/v/v) mixtures of H₂O, amine, and compound were prepared as described for comparative example 1.

A 3:3:1 (v/v/v) mixture of H₂O, ethanolamine, and THF was observed to be a single phase solution. This solution separated into two phases after CO₂ was bubbled through the liquid mixture for 30 minutes, with an aqueous phase and a non-aqueous phase comprising THF. However, the two separate phases did not recombine into one miscible layer even after N₂ was bubbled through the liquid mixture for 90 minutes at 50° C.

A 3:3:1 (v/v/v) mixture of H₂O, ethanolamine, and DMSO was observed to be a single phase solution. This solution did not separate into two phases after CO₂ was bubbled through the liquid mixture for 120 minutes, however turbidity was observed.

A 3:3:1 (v/v/v) mixture of H₂O, 2-(methylamino)ethanol, and THF was observed to be a single phase solution. This solution separated into two phases after CO₂ was bubbled through the liquid mixture for 10 minutes, with an aqueous phase and a non-aqueous phase comprising THF. However, the two separate phases did not recombine into one miscible layer even N₂ was bubbled through the liquid mixture for 90 minutes at 50° C.

Thus, in preliminary studies, certain primary and secondary amine additives did not exhibit reversible switchable of ionic strength character. Although they switched from lower ionic strength to higher ionic strength, they were not successfully switched from higher to lower ionic strength forms using the low energy input conditions of bubbling N₂ through the liquid mixture for 90 minutes at 50° C. It is noted that higher temperatures were not used due to the limitation posed by the boiling point of THF of 66° C. Bubbling N₂ at a higher temperature may have led to the reverse reaction; however, THF evaporation would have been a problem. Although not wishing to be bound by theory the inventors suggest that this irreversibility may be as a result of carbamate formation arising from the reaction of available N—H groups in the primary and secondary amines with CO₂. The removal of carbamate ions in water to give non-ionic amines by heating and bubbling a nonreactive gas can be difficult.

Example 1: Reversible Solvent Switching in Tertiary Amine/Water Systems

Three tertiary amines, DMAE, MDEA and THEED were investigated as additives for switchable ionic strength solutions. DMAE and MDEA are monoamines, and THEED is a diamine.

Six dram vials containing a magnetic stirrer and fitted with a rubber septa were prepared with 1:1:1 w/w/w solutions of water, THF, and an additive of tertiary amine compound of formula (1). To introduce gas to the solution, a single narrow gauge steel needle was inserted and gas was bubbled through. A second narrow gauge steel needle was inserted to allow venting of the gaseous phase.

The solutions were tested for switchable ionic strength character by bubbling CO₂ through the mixtures. The time necessary to observe separation of the THF from the aqueous solution of the ionic bicarbonate salt was recorded and is shown in Table 1 below. It was determined that it typically takes 30 min of bubbling with CO₂ to separate out THF from the aqueous phase.

TABLE 1 Duration of CO₂ bubbling required to separate THF from aqueous phase comprising additive, and duration of N₂ bubbling required to recombine THF and the aqueous phase Time of CO₂ bubbling to Time of N₂ bubbling to get phase separation get phase recombination Additive at 25° C. RT (min) at 50° C. (min) DMAE ~30 ~90 MDEA ~30 ~30 THEED ~30 ~60

After separation of the THF into a distinct non-aqueous phase was observed, nitrogen was then bubbled through the two-phase solutions at a temperature of 50° C. in order to remove CO₂ from the aqueous phase and switch at least a portion of the ionic bicarbonate salt form back to the non-ionic tertiary amine form. If the switching reaction was sufficiently reversible to reduce the ionic strength of the aqueous phase to a level allowing miscibility with the THF, conversion of the two-phase mixture to a single aqueous phase was observed.

As shown in Table 1, all of the tested tertiary amine additives could be switched back from their ionic forms allowing recombination of the two phase mixtures to a single phase.

Example 2: Quantitative Determination of the Separation of Compound and Additive Upon Switching

The three switchable aqueous solution systems of Example 1 were further investigated by ¹H NMR spectroscopy to quantify the amount of THF separated from the aqueous phase upon switching of the additive to its higher ionic strength ammonium bicarbonate form, and to quantify the amount of additive retained in the aqueous solution after switching.

To measure the extent of THF being forced out of an aqueous phase by an increase in ionic strength, and the amounts of amine which remained in the aqueous phase, 1:1:1 w/w/w solutions of water, THF, and amine additive were prepared in graduated cylinders and the cylinders were capped with rubber septa. After 30 minutes of bubbling CO₂ through the liquid phase at a flow rate of 3-5 mL min¹) as measured by a J&W Scientific ADM 2000 Intelligent Flow Meter, from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in d₃-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard.

¹H NMR spectra were acquired on a Bruker AV-400 NMR spectrometer at 400.3 MHz for several replicate solutions of each mixture, and through integration of the ethyl acetate standard, a concentration of THF or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase giving a percentage of the compound being forced out or retained. The results are shown in Table 2 below.

TABLE 2 Amount of THF separated out of aqueous phase comprising additive and amount of additive retained in the aqueous phase Amount of THF separated Amount of additive retained Additive (mol %) (mol %) DMAE 76 ± 1.7% 73.5 ± 2.0% MDEA 74 ± 3.0% 90.7 ± 1.5% THEED 67 ± 5.0% 98.6 ± 0.2%

The choice of tertiary amine additive was found to determine the amount of THF separated from the aqueous phase upon switching with CO₂ as shown in Table 2. When the tertiary amine was MDEA, 74 mol % of the THF was separated from the aqueous phase after bubbling CO₂ through the solution, while 90.7 mol % of the additive (in ionic form) was retained in the aqueous phase.

In some embodiments, it is preferred that substantially all of the additive remains in the aqueous phase, rather than going into the non-aqueous phase. This is because the utility of such solutions as reusable solvent systems would be increased if losses of the additive from the aqueous phase could be minimised. In the case of MDEA, 90.7 mol % of the MDEA remained in the aqueous phase. Thus, 9.3 mol % of the MDEA was transferred into the non-aqueous phase comprising THF. Interestingly, THEED had the best retention in the aqueous phase at approximately 98.6 mol %, even though it was least successful in forcing about 67.7 mol % of the THF out of solution.

Subsequent bubbling of N₂ through the mixture lowered the ionic strength and allowed the THF and aqueous phases to become miscible and recombine. At 50° C., this took about 30 minutes for the MDEA/THF/water mixture (Table 1). The rate of recombination would increase at higher temperatures, but this was not attempted in this case because of the low boiling point of THF (boiling point 66° C.).

These experiments were also conducted using air rather than nitrogen as the nonreactive gas to drive off CO₂ from the aqueous solution and switch at least a portion of the additive from ionic form to non-ionic form. The time taken for the recombination of the aqueous and non-aqueous phases was approximately the same for air as it was for N₂ for each additive.

Example 3: Quantitative Determination of the Separation of Compound and Additive Upon Switching at Different Additive Loadings

Reversible solvent switching in amine/water systems were explored for different loadings of five additives, while keeping the ratio of THF:water at a constant 1:1 w/w. The additives were all tertiary amines selected from monoamines DMAE and MDEA, diamine TMDAB, triamine DMAPAP and tetramine HMTETA.

To measure the extent of THF being forced out of an aqueous phase by an increase in ionic strength, and the amounts of amine which remained in the aqueous phase, 1:1 w/w solutions of water:THF were prepared in graduated cylinders and the appropriate amount of amine additive added. The graduated cylinders were capped with rubber septa. This comparison involved bubbling CO₂ through a single narrow gauge steel needle for 30 min at a rate of 3-5 mL min⁻¹ as measured by a J&W Scientific ADM 2000 Intelligent Flow Meter to switch the tertiary amine in aqueous solution with THF to ionic form. A second narrow gauge steel tube was provided to vent the gaseous phase. A visible phase separation into two liquid phases occurred, resulting in a non-aqueous and an aqueous phase. Aliquots of the non-aqueous and aqueous layers were taken and were spiked with a known amount of ethyl acetate to act as an internal standard and the amounts of THF and additive were quantified by ¹H NMR integration as discussed in Example 2. The results are shown in Table 3 below.

TABLE 3 Comparison of relative amounts of amine additive to the separation of THF from 1:1 w/w solutions of THF and H₂O and retention of amine in aqueous phase when reacted with CO₂. THF:H₂O:Additive % THF % Additive Additive (w/w/w) Separated^([a]) Retained^([a]) DMAE 1:1:1 76 ± 1.7% 73.5 ± 2.0% DMAE 3:3:1 85 ± 2.2% 93.9 ± 2.1% DMAE 5:5:1 74 ± 5.6% 91.7 ± 2.6% DMAE 10:10:1 75 ± 0.3% 98.3 ± 0.4% MDEA 1:1:1 74 ± 3.0% 90.7 ± 1.7% MDEA 3:3:1 74 ± 3.8% 95.7 ± 1.5% MDEA 5:5:1 72 ± 0.3% 95.2 ± 1.5% MDEA 10:10:1 66 ± 3.0% 96.6 ± 0.6% TMDAB 3:3:1 87 ± 1.3% 87.1 ± 2.1% TMDAB 5:5:1 87 ± 0.6% 99.6 ± 0.1% TMDAB 10:10:1 80 ± 0.5% 99.4 ± 0.1% TMDAB 15:15:1 74 ± 0.9% 98.4 ± 0.4% DMAPAP 3:3:1 78 ± 6.1% 87.1 ± 7.3% DMAPAP 5:5:1 81 ± 1.0% 98.4 ± 0.4% DMAPAP 10:10:1 69 ± 1.4% 96.0 ± 0.8% DMAPAP 15:15:1 62 ± 1.1% 94.4 ± 1.1% HMTETA 3:3:1 80 ± 4.0% 95.6 ± 1.5% HMTETA 5:5:1 80 ± 3.0% 98.4 ± 1.2% HMTETA 10:10:1 70 ± 1.3% 98.0 ± 1.0% HMTETA 15:15:1 65 ± 4.9% 98.2 ± 0.3% ^([a])Determined by ¹H NMR spectroscopy as discussed in Example 2.

It is apparent that an increase in the loading of the additive generally resulted in an increase in the % THF separated from the aqueous solution after switching, as would be expected. It can also be seen that the diamine compound TMDAB at a 9 wt % loading (i.e. 5:5:1 THF:H₂O:amine) forced 87% of the THF out of the aqueous phase after switching while 99.6% of the additive was retained in the aqueous phase. Even at a 3 wt % loading of TMDAB (15:15:1 THF:H₂O:amine), 74% of the THF was forced out after switching. In comparison, the monoprotonated additives DMAE and MDEA were only effective at higher loadings and had greater losses of the additive to the THF phase (Table 3).

In all experiments, the effect of the increase in ionic strength upon switching with CO₂ could be reversed; such that the THF phase recombined with the aqueous phase to regenerate a one phase system when the mixture was heated and sparged with N₂ or air to remove CO₂.

Example 4A: Qualititative Determination of the Separation of Selected Compound (THF) and Additive (Amine) Upon Switching at Equivalent Additive Loadings

A qualitative comparison of reversible solvent switching in the five amine/water systems of Example 3 was undertaken at equivalent additive loadings to determine by ¹H NMR spectroscopy the relative effectiveness of switching each additive from non-ionic amine to ionic ammonium bicarbonate and back to non-ionic amine forms. Aqueous solutions (0.80 molal) of DMAE, MDEA, TMDAB, THEED, DMAPAP, HMTETA additives were added to 1:1 w/w solutions of THF:D₂O in NMR tubes, which were sealed with rubber septa. ¹H NMR spectra were acquired for each sample prior to any gas treatment, and are shown as the A spectra in FIGS. 4, 5, 6, and 7 for DMAE, TMDAB, HMTETA and DMAPAP respectively. Two narrow gauge steel needles were inserted and the trigger gas was gently bubble through one of the needles into the solution at a rate of 4-5 bubbles per second. The second needle served as a vent for the gas phase, which was maintained at a positive pressure above atmospheric by the bubbling.

CO₂ was used as the trigger to switch the amine from its non-ionic to ionic form. ¹H NMR spectra were acquired for each sample after switching with CO₂.

The spectrum obtained after switching DMAE by 20 minutes of bubbling at 25° C. with a CO₂ trigger is shown as spectrum B in FIG. 4. Subsequently, the additive was switched back to non-ionic form by bubbling a nitrogen gas trigger through the solution for 300 minutes at 75° C. and the spectrum is shown as spectrum C in FIG. 4.

The spectrum obtained after switching TMDAB by 30 minutes of bubbling at 25° C. with a CO₂ trigger is shown as spectrum B in FIG. 5. Subsequently, the additive was switched back to non-ionic form by bubbling a nitrogen gas trigger through the solution for 240 minutes at 75° C. and the spectrum is shown as spectrum C in FIG. 5.

The spectrum obtained after switching HMTETA by 20 minutes of bubbling at 25° C. with a CO₂ trigger is shown as spectrum B in FIG. 6. Subsequently, the additive was switched back to non-ionic form by bubbling a nitrogen gas trigger through the solution for 240 minutes at 75° C. and the spectrum is shown as spectrum C in FIG. 6.

The spectrum obtained after switching DMAPAP by 20 minutes of bubbling at 25° C. with a CO₂ trigger is shown as spectrum B in FIG. 7. Subsequently, the additive was switched back to non-ionic form by bubbling a nitrogen gas trigger through the solution for 120 minutes at 75° C. and the spectrum is shown as spectrum C in FIG. 7.

Example 4B: Quantitative Determination of the Separation of Selected Compound (THF) and Additive (Amine) Upon Switching at Equivalent Additive Loadings

To measure the amount of THF being separated out of an aqueous phase by increasing its ionic strength, and the amounts of amine which remained in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. The appropriate mass of amine additive to result in a 0.80 molal solution was added and the cylinders were capped with rubber septa. After 30 minutes of bubbling CO₂ through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The two phases were a non-aqueous phase comprising THF, which was forced out of the increased ionic strength aqueous solution, and an aqueous phase comprising the additive in ionic form. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in d₃-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired as for the fully protonated additives, and through integration of the ethyl acetate standard, a concentration of THF or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase giving a percentage of the compound being forced out or retained. The results are shown in Table 4 below.

TABLE 4 Comparison of abilities of 0.80 molal aqueous solutions of amine additives to separate THF from 1:1 w/w solutions of THF and H₂O and retention of amine additive in the aqueous phase when reacted with CO₂ Additive % THF Separated^([a]) % Additive Retained^([a]) DMAE 70 ± 0.6% 98.0 ± 0.2% MDEA 61 ± 0.6% 99.0 ± 1.3% TMDAB 82 ± 0.6% 99.2 ± 0.4% DMAPAP 79 ± 1.2% 98.8 ± 0.4% HMTETA 78 ± 0.9% 99.3 ± 0.4% ^([a])Determined by ¹H NMR spectroscopy as discussed in Example 1.

Diamine TMDAB, triamine DMAPAP and tetramine HMTETA additives exhibited superior THF separation compared to monoamine additives DMAE and MDEA. This observation can be explained due to the increase in ionic strength as a result of the increased charge on the quaternary ammonium cations resulting from the protonation of multiple basic nitrogen centres in the diamine, triamine and tetramine. It is apparent from equation (C) that for an equimolal concentration of additive, an increase in the charge on the cation of the salt from +1 to +2 should give rise to a tripling in ionic strength.

It should be noted that although TMDAB and DMPAP contain more than two tertiary amine centres, only two of the basic sites in each molecule are capable of protonation as a result of switching with CO₂. This means that equimolal solutions of the protonated salts of TMDAB, DMAPAP and HMTETA should each exhibit a similar ionic strength, and thus similar % THF separations, as is apparent from Table 4.

Example 5: Reversible Protonation of Amine Additives in H₂O as Monitored by Conductivity

Protonation of aqueous solutions of three tertiary amine additives, DMAE, MDEA, and THEED, in response to the addition of a CO₂ trigger was performed and monitored by conductivity meter.

Aqueous solutions of an additive with distilled, deionised H₂O were prepared (1:1 v/v H₂O and DMAE, 1:1 v/v H₂O and MDEA and 1:1 w/w H₂O and THEED) in sample beakers. 1:1 w/w H₂O and THEED was used because a 1:1 v/v solution was too viscous to pour accurately. A trigger gas chosen from CO₂, air or nitrogen was bubbled at identical flow rates through the solution via a narrow gauge steel tube and the conductivity of the solution was measured periodically using a Jenway 470 Conductivity Meter (Bibby Scientific, NJ, US) having a cell constant of 1.02 cm⁻¹.

Results of bubbling a CO₂ gas trigger through the solutions of additives in water at room temperature are depicted in FIG. 7. As shown in this Figure, the conductivity of each of the additive solutions rose as the amine was converted to its ionic form as it was contacted with the CO₂ trigger. The aqueous solution of DMAE showed the largest rise in conductivity.

It is noted that conductivity is not simply a function of salt concentration; conductivity is also strongly affected by a solution's viscosity. Thus, even if two separate additive solutions have identical numbers of basic sites which can be fully protonated and have identical concentrations in water, they may have different conductivity levels.

The deprotonation reactions of the ionic solutions of additives in water were monitored in a similar manner, and the conductivity plot is shown in FIG. 8. Nitrogen gas was flushed through the solution at 80° C. to switch salts back to their non-ionic tertiary amine form. The residual levels of conductivity exhibited show that none of the additives were completely deprotonated by this treatment within 6 h.

Example 6: Reversible Protonation of Amine Additives in D₂O as Monitored by ¹H NMR Spectroscopy

The degree of protonation of tertiary amine additives upon contact with a CO₂ trigger was investigated by ¹H NMR spectroscopy. Two monoamines, DMAE and MDEA, and the diamine THEED were chosen for study.

In order to establish the chemical shifts of the protonated bases, molar equivalents of several strong acids, including HCl and HNO₃, were added to separate solutions of the amines dissolved in D₂O. ¹H NMR spectra were acquired on a Bruker AV-400 NMR spectrometer at 400.3 MHz for three replicate solutions of each amine. An average value of each chemical shift for each protonated base was calculated along with standard deviations. If the bases when reacted with the trigger to ionic form showed chemical shifts within this error range, they were considered to be 100% protonated within experimental error. The ¹H NMR chemical shifts of the unprotonated amines were also measured.

The extent of protonation by CO₂ of each additive at room temperature at 0.5 M (except THEED was at 0.1 M) in D₂O was monitored by ¹H NMR. The amine was dissolved in D₂O in an NMR tube and sealed with a rubber septa. The spectrum was then acquired. Subsequently, two narrow gauge steel needles were inserted and gas was gently bubbled through one of them into the solution at approximately 4-5 bubbles per second. The second needle served as a vent for the gaseous phase.

Firstly CO₂ was bubbled through the solution for the required length of time and then the spectrum was re-acquired. This process was repeated. The % protonation of the amine was determined from the observed chemical shifts by determining the amount of movement of the peaks from the normal position for the unprotonated amine towards the position expected for the fully protonated amine.

The results shown in FIG. 9 indicate that DMAE and MDEA are fully protonated (the peaks fell within the standard deviation of the HCl and HNO₃ salts) within 20 minutes when CO₂ was bubbled through the solution. THEED is one half protonated (49%) by 10 minutes, meaning that only one of the two nitrogen atoms of this diamine has been protonated.

The reverse reaction was monitored in a similar manner and the results shown in FIG. 10. Nitrogen gas was flushed through the solution at 75° C. The spectra showed that none of the additives were completely deprotonated by this treatment within 5 hours, (2 hours for THEED), with the ionic form of THEED reacting the fastest of the three, and with DMAE being the slowest. THEED was 98% deprotonated (i.e., the ionic strength of the solution dropped twenty-five fold) after 2 hours of N₂ bubbling.

The observed rates of switching, as represented by the protonation and deprotonation processes, are affected by the manner in which the CO₂ or sparging gas was introduced (e.g., its rate of introduction and the shape of the vessel containing the solution). For example, a comparison of FIG. 7 with FIG. 9 shows that the rate of the reaction in the ¹H NMR experiment was faster than that in the conductivity experiment. This rate difference is due to the difference in equipment. The ¹H NMR experiment was performed in a tall and narrow NMR tube, which is more efficiently flushed with CO₂ than the beaker used in the conductivity tests. Furthermore, it is very likely that the rate of deprotonation and thus reduction in the ionic strength of the solution could be increased if the N₂ sparging were done in a more efficient manner than simple bubbling through a narrow gauge tube.

Thus, a 1:1 v/v mixture of MDEA and water can be taken to 100% protonated and returned back to about 4.5% protonation by bubbling/sparging with N₂. It is possible to calculate an approximate ionic strength of the 100% and 4.5% degrees of protonation of the amine additive. The density of MDEA is 1.038 g/mL, so a 1 L sample of this mixture would contain 500 g of water and 519 g (4.4 mol) MDEA. Therefore the concentration of MDEA is 4.4 M. The ionic strength, assuming an ideal solution and assuming that the volume does not change when CO₂ is bubbled through the solution, is 4.4 M at 100% protonation and 0.198 M at 4.5% protonation (using equation (A) above).

Example 7: Reversible Protonation of Amine Additives in H₂O as Monitored by Conductivity

Three tertiary polyamine additives were selected for further investigation of additives for switchable ionic strength aqueous solutions. TMDAB is a diamine, DMAPAP is a triamine, and HMTETA is a tetramine.

1:1 v/v solutions of the various additives and distilled, deionised water were prepared in six dram glass vials and transferred to a fritted glass apparatus which acted as a reaction vessel. The fritted glass apparatus consisted of a long narrow glass tube leading to a fine glass frit having a diameter of approximately 4 cm. The other end of the glass frit was connected to a cylindrical glass tube which held the solution of the additive during contacting with the trigger gas. This apparatus allowed a multiple source of trigger gas bubbles to contact the solution, compared to the single point source of Example 5.

A trigger gas chosen from CO₂, air or nitrogen was bubbled through the solution via the glass frit at a flow rate of 110 mL min⁻¹ as measured by a J&W Scientific ADM 2000 Intelligent Flowmeter (CA, USA). For each conductivity measurement, the solution was transferred back to a six dram vial, cooled to 298 K and measured in triplicate. Conductivity measurements were performed using a Jenway 470 Conductivity Meter (Bibby Scientific, NJ, US) having a cell constant of 1.02 cm⁻¹.

FIG. 11 shows a plot of the conductivity changes resulting from bubbling CO₂ through the three solutions at 25° C. It is apparent that HMTETA (▪) and DMAPAP (▴), the tetramine and triamine respectively, exhibit lower conductivities than TMDAB (♦), the diamine. In addition, TMDAB exhibits the highest rate of conductivity increase.

The reverse reaction was monitored in a similar manner and the results shown in FIG. 12. Nitrogen gas was flushed through the solution at 80° C. It is apparent that the conductivity of the solution of HMTETA (▪) in ionic form returns to close to zero after 20 minutes, indicating substantial removal of CO₂ from the solution and reversion of the additive to its non-ionic form. The rate of conductivity decrease is highest for TMDAB (♦), the diamine, indicating it can be reversibly switched between non-ionic and ionic forms at a higher rate than HMTETA and DMAPAP (▴)

The observed rates of switching, as represented by the changes in conductivity, appear to be affected by the manner in which the CO₂ or sparging gas was introduced (e.g., its rate of introduction and the shape of the vessel containing the solution). For example, a comparison of FIG. 11 with FIG. 7 shows that the rate of the reaction utilising the fritted gas apparatus appears to be faster than that the delivery of the trigger via a narrow gauge steel tube, although it is accepted that different additives are being compared. This may be because the fritted glass apparatus is more efficiently flushed with CO₂ than the beaker used in the conductivity tests.

Example 8: Emulsion Formation and Disruption of Solutions Comprising a Surfactant and Switchable Amine Additive

Three vials were prepared, each containing 0.462 g N,N,N′,N′-tetramethyl-1,4-diaminobutane (TMDAB) in 4 mL water (giving a 0.80 molal solution) and 20 mg SDS (sodium dodecyl sulfate, a nonswitchable surfactant) at 0.50 wt % loading. To each vial n-decanol (0.25 mL) was added and the vials were capped with rubber septa. FIG. 13, photograph “A” shows the three vials at this stage in the experiment. In each vial, there are two liquid phases. The lower liquid aqueous phase has a larger volume and is transparent and colourless. The upper liquid n-decanol phase has a smaller volume and is also colourless though is not as transparent. n-Decanol is not miscible with neat water.

The three vials were then shaken by hand for 30 seconds. FIG. 13, photograph “B” shows the appearance after the shaking. All three vials show an opaque liquid mixture with cloudiness and foaming typical of an emulsion, which is as expected because of the presence of the known surfactant SDS.

Gases were then bubbled through the solutions for 30 min via a narrow gauge steel needle inserted through the septum and down into the liquid mixture. For each vial, gas was allowed to vent out of the vial via a short second needle inserted into the septum but not into the liquid phase. The gas was CO₂ for the left vial and N₂ for the centre and right vials. FIG. 13, photograph “C” shows the appearance after the treatment with gas. Only the right two vials show the cloudiness typical of an emulsion. The liquid in the left vial is now clear and free of foam, showing that the conversion of the aqueous solution to its high-ionic strength form has greatly weakened the ability of the SDS to stabilize emulsions and foams. The liquid contents of the centre and right vials still show the cloudiness and foaminess typical of an emulsion, indicating that bubbling N₂ gas through the solution does not have the effect of weakening the ability of SDS to stabilize emulsions and foams. This is because N₂ had no effect on the ionic strength of the aqueous phase.

While the left vial was allowed to sit for 30 min without further treatment, CO₂ gas was bubbled through the liquid phase of the centre vial for 30 min and N₂ was bubbled through the right vial. FIG. 13, photo “D” shows the appearance of the three vials after this time. The liquids in the left and centre vials are now largely clear and free of foam, showing that the conversion of the aqueous solution to its high-ionic strength form has greatly weakened the ability of the SDS to stabilize emulsions and foams. The emulsion and foam still persist in the right vial.

N₂ gas was bubbled through the liquid phases of the left and centre vials for 90 min in order to remove CO₂ from the system and thereby lower the ionic strength of the aqueous solution. The two vials were then shaken for 30 min. During this gas treatment and shaking, the right vial was left untouched. FIG. 13, photograph “E” shows the appearance of the three vials after this time. All three exhibit the cloudiness typical of an emulsion, although foaminess in the left two vials is not evident, presumably because the conversion of the aqueous solution back to a low ionic strength is not complete. In practice, substantial conversion to low ionic strength is not difficult. However, it can be more difficult to achieve complete conversion.

Example 9: Description of Ionic Strength

The ionic strength of an aqueous solution of the salt will vary depending upon the concentration of the salt and the charge on the ammonium ion. For example, an amine B having n sites which can be protonated by carbonic acid to provide a quaternary ammonium cation of formula [BH_(n) ^(n+)], may have a switching reaction shown in reaction (1): B+nH₂O+nCO₂⇄[BH_(n) ^(n)+]+n[^(−O) ₃CH]  reaction (1)

If the molality of the amine in aqueous solution is m, the ionic strength I of the ionic solution after switching can be calculated from equation (C): I=½m(n ² +n)  (C)

Thus, for a given molality m, the ionic strength of a diprotonated diamine (n=2) will be three times that of a monoprotonated monoamine (n=1). Similarly, the ionic strength of a triprotonated triamine (n=3) will be six times that of that of a monoprotonated monoamine and the ionic strength of a tetraprotonated tetramine (n=4) will be ten times that of a monoprotonated monoamine. Thus, by increasing the number of tertiary amine sites in the compound of formula (1) which can be protonated by the trigger, the ionic strength of a solution comprising the corresponding salt of formula (2) can be increased, for a given concentration.

Not all the basic sites on a compound of formula (1) may be capable of protonation by a gas which generates hydrogen ions in contact with water. For instance, when the gas is CO₂, the equilibrium between CO₂ and water and the dissociated carbonic acid, H₂CO₃ is shown in reaction (2): CO₂+H₂O⇄H⁺+HCO₃ ⁻  reaction (2)

The equilibrium constant, K_(a) for this acid dissociation is calculated from the ratio

$\frac{\left\lbrack H^{+} \right\rbrack\left\lbrack {HCO}_{3}^{-} \right\rbrack}{\left\lbrack {CO}_{2} \right\rbrack}$ at equilibrium—in dilute solutions the concentration of water is essentially constant and so can be omitted from the calculation. The equilibrium constant K_(a) is conventionally converted into the corresponding pK_(a) value by equation (D): pK _(a)=−log K _(a)  (D)

The pK_(a) for reaction (2) is 6.36. The corresponding equilibrium for the dissociation of a protonated amine base BH⁺ (i.e. the conjugate acid) is provided by reaction (3), BH⁺⇄H⁺+B  reaction (3)

The equilibrium constant K_(aH), for the conjugate acid BH⁺ dissociation is calculated by the ratio

$\frac{\lbrack B\rbrack\left\lbrack H^{+} \right\rbrack}{\left\lbrack {BH}^{+} \right\rbrack}.$ The equilibrium constant K_(aH) is conventionally converted into the corresponding pK_(aH) value analogously to equation (D). From the foregoing, it will be apparent that the equilibrium constant for the switching reaction shown in reaction (1) above in which n=1 can be calculated from the ratio

$\frac{\left\lbrack {BH}^{+} \right\rbrack\left\lbrack {HCO}_{3}^{-} \right\rbrack}{\lbrack B\rbrack\left\lbrack {CO}_{2} \right\rbrack},$ which is equivalent to

$\frac{K_{a}}{K_{aH}}.$ The ratio

$\frac{K_{a}}{K_{aH}}$ can also be expressed in terms of the corresponding pK values as 10^(pK) ^(aH) ^(−pK) ^(a) . Thus, in the case of the dissociation of CO₂ in water, if the pK_(aH) value of the conjugate acid BH⁺ exceeds 6.36, the ratio

$\frac{\left\lbrack {BH}^{+} \right\rbrack\left\lbrack {HCO}_{3}^{-} \right\rbrack}{\lbrack B\rbrack\left\lbrack {CO}_{2} \right\rbrack}$ is greater than 1, favoring the production of ammonium bicarbonate. Thus, it is preferred that a salt as used herein comprises at least one quaternary ammonium site having a pK_(aH) greater than 6 and less than 14. Some embodiments have at least one quaternary ammonium site having a pK_(aH) in a range of about 7 to about 13. In some embodiments the salt comprises at least one quaternary ammonium site having a pK_(aH) in a range of about 7 to about 11. In other embodiments, the salt comprises at least one quaternary ammonium site having a pK_(aH) in a range of about 7.8 to about 10.5.

Example 10: Synthesis of Diamine and Triamine Switchable Additives Example 10A: Synthesis of N,N,N′,N′-tetraethyl-1,4-diaminobutane (TEDAB)

4.658 g (63.4 mmol) diethylamine was dissolved in 100 mL dichloromethane and cooled to 0° C. 2.339 g (15.1 mmol) succinyl chloride was added dropwise to the solution. The solution was warmed to room temperature and stirred for 18 hours.

An aqueous solution 0.80 mL concentrated HCl and 25 mL H₂O was added to the mixture to wash the organic layer. The organic layer was then removed and dried with MgSO₄. The solvent was removed in vacuo to yield 3.443 g of N,N,N′,N′-tetraethylsuccinamide in 99% yield. ¹H NMR (400 MHz CDCl₃) −δ: 3.37 (q, =7 Hz, 8H), 2.69 (s, 4H), 1.20 (t, J=7 Hz, 6H), 1.11 (t, J=7 Hz, 6H).

3.443 g (15.1 mmol) of N,N,N′,N′-tetraethylsuccinamide is dissolved in 100 mL THF, degassed with N₂ and cooled to 0° C. 61.0 mL of 2.0M LiAlH₄ in THF solution (122 mmol) was added dropwise to the solution. The solution was then refluxed for 6 hours.

The solution was then cooled to 0° C. and the excess LiAlH₄ was quenched by adding 4.6 mL H₂O, 4.6 ml, 15% NaOH, and 13.8 mL H₂O. The solution was warmed to room temperature and stirred for 12 hours. The precipitate was filtered off and washed with THF. The washings were combined with the original THF solution and dried with MgSO₄. The solvent was removed in vacuo to yield 2.558 g of a brown liquid resulting in a 84.6% yield of N,N,N′,N′-tetraethyl-1,4-diaminobutane. ¹H NMR (400 MHz CDCl₃) −δ: 2.55 (q, =7 Hz, 8H), 2.41 (t, J=7 Hz, 4H), 1.43 (t, J=7 Hz, 4H), 1.02 (t, J=7 Hz, 12H).

All other straight chain diamines, N,N,N′,N′-tetrapropyl-1,4-diaminobutane and N,N′-diethyl-N,N′-dipropyl-1,4-diaminobutane, were synthesized in a similar fashion utilizing the appropriate starting materials. Succinyl chloride, diethylamine, dipropylamine, lithium aluminum hydride solution were all purchased from Sigma Aldrich and used as received. N-ethylpropylamine was purchased from Alfa Aesar and the solvents and MgSO₄ were purchased from Fisher and used as received.

Example 10B: Synthesis of 1,1′,1″-(cyclohexane-1,3,5-triyl)tris(N,N-dimethylmethanamine) (CHTDMA)

1.997 g (9.2 mmol) 1,3,5-cyclohexane-tricarboxylic acid was taken up in 40 mL dichloromethane to create a suspension. 3.84 g (29.8 mmol) oxalyl chloride and one drop of DMF were added to the solution. The solution was refluxed for 3 hours, giving a yellow solution with white precipitate. The mixture was cooled to room temperature and the solvent was removed in vacuo resulting in 2.509 g of a solid which contained both the desired 1,3,5-cyclohexane tricarbonyl trichloride and unwanted salts. ¹H NMR (400 MHz CDCl₃) −δ: 2.88 (t, J=9 Hz, 3H), 2.69 (d, J=13 Hz, 3H), 1.43 (q, J=13 Hz, 3H).

2.509 g of the solid mixture was taken up in 50 mL THF and cooled to 0° C. 34.5 mL of a 2.0 M dimethylamine solution in THF (69 mmol) was added. The solution was warmed to room temperature and stirred for 18 hours. The solvent was then removed in vacuo leaving a yellow solid. The solid was taken up in a solution of 2.081 g (37.1 mmol) KOH in 20 mL H₂O. Organic contents were then extracted with 3×40 mL chloroform washings. The organic washings were collected and the solvent removed in vacuo to yield 1.930 g of a yellow liquid, N,N,N′,N′,N″,N″-hexamethylcyclohexane-1,3,5-tricarboxamide in 70.2% yield. ¹H NMR (400 MHz CDCl₃) −δ: 3.06 (s, 9H), 2.92 (s, 9H), 2.65 (q, J=15 Hz, 3H), 1.86 (t, J=8 Hz, 6H).

1.930 g (6.5 mmol) of N,N,N′,N′,N″,N″-hexamethylcyclohexane-1,3,5-tricarboxamide was dissolved in 80 mL THF and cooled to 0° C. 42.0 mL of 2.0M LiAlH₄ in THF solution (84 mmol) was added dropwise to the solution. The solution was then refluxed for 6 hours.

The solution was then cooled to 0° C. and the excess LiAlH₄ was quenched by adding 3.2 mL H₂O, 3.2 mL 15% NaOH, and 9.6 mL H₂O. The solution was warmed to room temperature and stirred for 12 hours. The precipitate was filtered off and washed with THF. The washings were combined with the original solution and dried with MgSO₄. The solvent was removed in vacuo to yield 1.285 g of a yellow liquid resulting in a 54.4% yield of 1,1′,1″-(cyclohexane-1,3,5-triyl)tris(N,N-dimethylmethanmine). ¹H NMR (400 MHz CDCl₃) −δ: 2.18 (s, 18H), 2.07 (d, J=7 Hz, 8H), 1.89 (d, J=12 Hz, 3H), 1.52, (m, J=7 Hz, 3H), 0.48 (q, J=12 Hz, 3H). M⁺=255.2678, Expected=255.2674.

Other cyclic triamines, N,N,N′,N′,N″,N″-1,3,5-benzenetrimethanamine, were synthesized in a similar fashion utilizing the appropriate starting materials. 1,3,5-benzenetricarbonyl trichloride was purchased from Sigma Aldrich and used as received. 1,3,5-cyclohexanetricarboxylic acid was purchased from TCI and used as received.

Example 11: Controlling the Zeta Potential of Suspended Clay Particles in Water

In a suspension of solid particles in a liquid, a zeta potential near to zero indicates that the particles have little effective surface charge and therefore the particles will not be repelled by each other. The particles will then naturally stick to each other, causing coagulation, increase in particle size, and either settle to the bottom of the container or float to the top of the liquid. Thus the suspension will not normally be stable if the zeta potential is near zero. Therefore having the ability to bring a zeta potential close to zero is useful for destabilizing suspensions such as clay-in-water suspensions. However, strategies such as addition of calcium salts or other salts are sometimes undesirable because, while these strategies do cause the destabilization of suspensions, the change in water chemistry is essentially permanent; the water cannot be re-used for the original application because the presence of added salts interferes with the original application. Therefore there is a need for a method for destabilizing suspensions that is reversible.

Experimental Methods:

Clay fines were weighed and placed into individual vials (0.025 g, Ward's Natural Science Establishment). Kaolinite and montmorillonite were used as received, but illite clay was ground into a powder using a mortar and pestle. Solutions containing additives were made with deionized water (18.2 MΩ/cm, Millipore) and 10 mL was added to the clay fines. A suspension was created using a vortex mixer and subsequently dispensed into a folded capillary cell. The zeta potential was measured using a Malvern Zetasizer instrument. The errors reported on the zeta potential values were the standard deviations of the zeta potential peaks measured.

Unless specified, all carbon dioxide treatments were conducted with the aqueous solutions prior to addition to the clay fines. For applicable measurements, ultra pure carbon dioxide (Supercritical CO₂ Chromatographic Grade, Paxair) was bubbled through the solutions using a syringe.

Results:

Illite

Additive Zeta Potential (mV) 0.8 molal BDMAPAP −19.1 ± 3.92 0.8 molal BDMAPAP + 1 h CO₂ −1.87 0.8 molal TMDAB −26.0 ± 3.92 0.8 molal TMDAB + 1 h CO₂ −4.56 1 mM TMDAB −39.5 ± 6.32 1 mM TMDAB + 1.5 hour CO₂ −4.69 ± 4.23 10 mM TMDAB −48.2 ± 7.44 10 mM TMDAB + 1.5 hour CO₂ −3.12 ± 7.16 Kaolinite

Additive Zeta Potential (mV) 0.8 molal BDMAPAP −24.3 ± 2.29 0.8 molal BDMAPAP + 1 h CO₂ −3.99 0.8 molal TMDAB −17.4 ± 3.92 0.8 molal TMDAB + 1 h CO₂   2.29 1 mM TMDAB −39.6 ± 6.68 1 mM TMDAB + 1.5 hour CO₂ −5.03 ± 4.46 10 mM TMDAB −50.7 ± 13.1 10 mM TMDAB + 1.5 hour CO₂ −3.35 ± 8.49 Montmorillonite

Additive Zeta Potential (mV) 0.8 molal BDMAPAP −16.8 ± 4.64 0.8 molal BDMAPAP + 1 h CO₂ −2.99 0.8 molal TMDAB −25.8 ± 4.14 0.8 molal TMDAB + 1 h CO₂ −5.52 1 mM TMDAB −40.2 ± 6.87 1 mM TMDAB + 1.5 hour CO₂ −3.20 ± 4.61 10 mM TMDAB −23.6 ± 5.68 10 mM TMDAB + 1.5 hour CO₂   9.07 ± 4.18

For three of the clays tested, it was found that switchable water additives TMDAB and BDMAPAP were effective additives for changing clay zeta potentials. Upon addition of CO₂, the absolute values of the clay zeta potentials were reduced. This effect was observed even at low concentrations of the switchable water additive (1 mM).

The data above demonstrates the ability of switchable water to affect the zeta potential of clay suspensions, however, the CO₂ treatments were conducted on the aqueous solutions of TMDAB before the clay fines were added (a method referred to as “switching externally”). Another experiment was performed in which CO₂ was bubbled through a 1 mM aqueous solution of TMDAB that already contained clay fines (a method referred to as “switching in situ”). The results with kaolinite clay are summarized in the table below.

Kaolinite Clay

Zeta Potential (mV) Switching Switching externally in situ 1 mM TMDAB −39.6 ± 6.68 −38.9 ± 8.69 1 mM TMDAB + 1 h CO₂ −5.03 ± 4.46 −0.31 ± 4.15 1 mM TMDAB + 1 h CO₂ + 1.5 h N₂ −25.0 ± 5.84 −32.5 ± 6.38 at 70° C.

It was observed that the magnitude of the zeta potential of the clay surfaces decreased regardless of whether the switching externally method or the switching in situ method was used. In addition, the zeta potential could be restored to its original value upon treatment with nitrogen gas at 70° C.

Example 12: Reversible Destabilization of a Clay-in-Water Suspension

Three variations of clay settling experiments were conducted with 1 mM TMDAB (TCI America, Batch FIB01) to elucidate the ability of this switchable ionic strength additive to affect stability of clay suspensions.

Experiment 1

As depicted in FIG. 14A, Kaolinite clay fines (5 g) were added to 100 mL of 1 mM TMDAB in deionized water. The mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder, which was subsequently sealed with a rubber septum. Settling of the clay fines was monitored as a function of time using a cathetometer.

CO₂ was bubbled through 100 mL of 1 mM TMDAB using a dispersion tube for 1 hour. Kaolinite fines (5 g) were added to the aqueous solution and the mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder and sealing with a rubber septum. Settling of clay fines was monitored. CO₂ was bubbled through 100 mL of 1 mM TMDAB using a dispersion tube for 1 hour. The solution was heated to 70° C. and N₂ was bubbled through for 1 hour. After cooling to room temperature, kaolinite fines (5 g) were added and the mixture was stirred 900 rpm for 15 minutes prior to transferring into a 100 mL graduated cylinder and sealing with a rubber septum. Settling of clay fines was monitored.

Experiment 2

As depicted in FIG. 14B, Kaolinite clay fines (5 g, Ward's Natural Science Establishment) were added to 100 mL of 1 mM TMDAB in deionized water. The mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder, which was subsequently sealed with a rubber septum. Settling of the clay fines was monitored as a function of time.

CO₂ was bubbled through the suspension above. The mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder, which was subsequently sealed with a rubber septum. Settling of the clay fines was monitored.

The clay fines above were resuspended in the solution and the mixture was heated to 70° C. N₂ was bubbled through for 1 hour. After cooling to room temperature, the mixture was stirred 900 rpm for 15 minutes prior to transferring into a 100 mL graduated cylinder and sealing with a rubber septum. Settling of clay fines was monitored.

Experiment 3

As depicted in FIG. 14C, Kaolinite clay fines (5 g, Ward's Natural Science Establishment) were added to 100 mL of 1 mM TMDAB in deionized water. The mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder, which was subsequently sealed with a rubber septum. Settling of the clay fines was monitored as a function of time.

The suspension above was filtered. CO₂ was bubbled through the filtrate for 1 hour. Kaolinite clay fines (4.5 g) were added and the mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder, which was subsequently sealed with a rubber septum. Settling of clay fines was monitored.

Control Experiment

CO₂ was bubbled through 100 mL of deionized water for 1 h. Kaolinite clay (5 g) was added and the mixture was stirred for 15 minutes at 900 rpm prior to transferring into a 100 mL graduated cylinder, which was subsequently sealed with a rubber septum. Settling of clay fines was monitored.

Results

Experiment 1 was conducted to examine the effect of the switchable water additive on the settling behavior of clay. The switching was conducted in the absence of clay to ensure that the switching occurred fully without any impedance from the clay. The results are plotted in FIGS. 15A-C.

A stable suspension was formed with kaolinite clay and 1 mM TMDAB. However, kaolinite clay with 1 mM of CO₂ treated TMDAB resulted in the settling of clay with a clean supernatant and a clear sediment line. A stable suspension was also formed with kaolinite clay and 1 mM of TMDAB treated for 1 hour with CO₂ followed by 1 hour of N₂ treatment. Photographs were taken after each 1 hour treatment and are provided in FIG. 15D.

Experiment 2 was conducted to examine if the switchable water additives would still switch upon addition of CO₂ in the presence of kaolinite clay.

Kaolinite clay and 1 mM TMDAB were initially mixed to give a stable suspension. This suspension was treated with CO₂, which resulted in the settling of the clay fines with a clean supernatant and a clear sediment line. As shown in FIGS. 16A-B, the behavior observed was exactly as that observed for Experiment 1. The settled clay was stirred to reform a suspension, which was treated with N₂, after which the suspension was stable. Experiment 3 was conducted to determine if the switchable ionic strength additive adheres to the clay surface and would therefore be lost upon removal of the clay. The suspension created with the CO₂ treated filtrate settled much like the previous two experiments. A clear sediment line was observed, however, the liquid above the sediment line was turbid and still contained clay fines (See, FIGS. 17A and C). This behavior was also observed with deionized water treated with CO₂ in the absence of any switchable water additive (See, FIGS. 17B and C).

Example 13: The Removal of Water from an Organic Liquid

2.710 g THF (3.76×10⁻² mol) and 0.342 g H₂O (1.90×10⁻² mol) were mixed together in a graduated cylinder to create a single phase solution of roughly 8:1 THF:H₂O (w/w). 0.109 g (7.56×10⁻⁴ mol) of N,N,N′N′-tetramethyl-1,4-diaminobutane (TMDAB) was added to the solution again generating a single phase solution. The THF:TMDAB ratio was approximately 25:1 (w/w). This solution containing three components had a mol % composition as follows: 65.6 mol % THF, 33.1 mol % H₂O, and 1.3 mol % TMDAB.

A stir bar was added to the solution in the graduated cylinder and the cylinder was capped with a rubber septa. A long narrow gauge steel needle was inserted through the septa and into the solution. A second needle was pushed through the septa but not into the solution. CO₂ was bubbled into the solution through the first steel needle at a flow rate of about 5 mL min⁻¹ with stirring of ˜300 RPM for 30 minutes. At the end of the bubbling a clear, colourless aqueous phase at the bottom of the cylinder had creamed out of the original organic phase. The organic phase was separated from the aqueous phase by decantation.

76.1 mg of the top organic phase was extracted and placed in an NMR tube. The sample was diluted with deuterated acetonitrile and 32.3 mg of ethyl acetate was added to act as an internal standard. A ¹H NMR spectrum was acquired. Using the integration of the NMR signals of the H₂O and TMDAB compared to those of the known amount of ethyl acetate added, calculated masses of 4.58 mg and 0.46 mg of H₂O and TMDAB were acquired respectively. The remaining mass of 71.06 mg corresponds to the THF in the sample.

The “dried” organic THF phase had a mol % composition as follows: 79.3 mol % THF, 20.5 mol % H₂O and 0.3 mol % TMDAB.

Example 14: Use of a Switchable Additive to Expel an Organic Compound Out of Water and then the Removal of Much of the Additive from the Aqueous Phase

In some embodiments, the non-ionized form of the additive is water-immiscible. This makes it possible to create high ionic strength in the water, while CO₂ is present, in order to achieve some purpose such as the expulsion of an organic compound from the aqueous phase and then, by removing the CO₂, to recover the majority of the additive from the water. Here we describe the expulsion of THF from a water/THF mixture and subsequent recovery of much of the additive from the water.

1.50 g H₂O, 1.50 g THF, and 0.30 g N,N,N′N′-tetraethyl-1,4-diaminobutane (TEDAB) were mixed together in a graduated cylinder to generate a single phase solution. The solution had a total volume of 3.54 mL. A small stir bar was added to the solution and the cylinder was capped with a rubber septa. The following procedure was run in triplicate with a new sample (of the same contents shown above) each time.

A long, narrow gauge needle was inserted through the septa into the solution. A second small needle was inserted into the septa but not into the solution itself. CO₂ was bubbled through the solution a flow rate of about 5 ml/min for 45 minutes with stirring until a 2^(nd) phase creams out on top of the aqueous phase. The CO₂ bubbling was stopped and the needles withdrawn. The cylinder was immersed in a hot water bath for several seconds to facilitate the separation of the liquid phases. Both phases were clear and yellow in colour. The top organic layer had a volume of 1.50 mL and the remaining aqueous layer had a volume of 2.04 mL.

The organic phase was decanted off giving a mass of 1.253 g (density=0.84 g/mL). The aqueous phase had a mass of 1.94 g (density=0.98 g/mL) resulting in a loss of 0.12 g due to transferring of solutions or blow-off.

A 39.1 mg sample of the organic phase was placed in an NMR tube with deuterated acetonitrile and 50.2 mg ethyl acetate to act as an internal standard. A 66.2 mg sample of the aqueous phase was placed in a 2^(nd) NMR tube with deuterated acetonitrile with 22.3 mg ethyl acetate to act as an internal standard. A ¹H NMR spectra was acquired and knowing the corresponding amount of ethyl acetate in each sample the resulting amounts of THF in the aqueous sample and additive in the organic sample can be calculated. Knowing the mass, volume, and density of each layer, the total amount of THF or additive in a respective layer can be calculated.

It was found that an average of 77.2±3.5% THF was removed from the aqueous phase with 91.1±3.7% of the TEDAB residing in the aqueous phase.

1.943 g (1.90 mL) of the aqueous phase was returned to the same graduated cylinder. The needles and septa were put back into the cylinder and the cylinder was immersed in a 60° C. water bath. N₂ was introduced in the same fashion as CO₂ performed previously and the N₂ was bubbled through the solution for 90 minutes causing a deep yellow organic phase to cream out of the aqueous phase.

The new organic phase had a volume of 0.17 mL leaving an aqueous phase of 1.57 mL. The organic layer was decanted off giving a mass of 0.09 g while the remaining aqueous phase had a mass of 1.507 g (density=0.96 g/mL). A 37.9 mg sample of the aqueous phase was taken up in an NMR tube with deuterated acetonitrile and 41.5 mg ethyl acetate to act as an internal standard. A ¹H NMR spectra was acquired and using the same procedure of comparing integrations as performed above, it was found that 49.3±6.3% of the TEDAB was removed from the aqueous phase. It was also found that the overall 90.0±2.1% of the total THF had been removed from the aqueous phase at the end of the procedure.

Using N,N′-diethyl-N,N′-dipropyl-1,4-diaminobutane instead of N,N,N′N′-tetraethyl-1,4-diaminobutane (TEDAB) in the above procedure caused the expulsion of 68% of the THF from the aqueous phase after CO₂ treatment. After N₂ treatment of the separated aqueous phase, 81% of the N,N′-diethyl-N,N′-dipropyl-1,4-diaminobutane was removed from the aqueous phase.

Example 15: Determining the Miscibility of Several Diamines and Triamines with Water in the Presence and Absence of CO₂

In some embodiments, the non-ionized form of the additive is water-immiscible while the charged form is water-miscible or water-soluble. The following experiments were performed in order to identify whether certain diamines and triamines have this phase behavior.

A 5:1 w/w solution of water and the liquid additive (total volume 5 mL) were mixed together in a glass vial at room temperature. Whether the mixture formed one or two liquid phases was visually observed. Then CO₂ was bubbled through the mixture via a single narrow gauge steel needle at a flow rate of ˜5 mL min⁻¹ for 90 min. Whether the mixture formed one or two phases was visually observed. The results were as follows:

Before addition After addition Additive of CO₂ of CO₂ 1,3,5-C₆H₃(CH₂NMe₂)₃ miscible miscible 1,3,5-cycloC₆H₉(CH₂NMe₂)₃ immiscible miscible Et₂NCH₂CH₂CH₂CH₂NEt₂ immiscible miscible PrEtNCH₂CH₂CH₂CH₂NPrEt immiscible miscible Pr₂NCH₂CH₂CH₂CH₂NPr₂ immiscible immiscible

Example 16: Preparation and Use of a Polyamine for Expulsion of Acetonitrile from Water Example 16A: Preparation of the Polyamine

Polyethyleneimine samples of three different molecular weights (M.W. 600, 99%; M.W. 1800, 99%; and M.W. 10,000, 99%) were purchased from Alfa Aesar. Formaldehyde (37% in H₂O) and formic acid were purchased from Sigma-Aldrich. All reagents were used without further purification. Amberlite™ IRA-400 (OH) ion exchange resin was purchased from Supelco.

For the samples using polyethyleneimine M.W. 600 and 1800: A 250 mL round bottom flask was equipped with a 2 cm teflon stirring bar and placed over a magnetic stirring plate. 1.8 g (M.W. 600: 41.9 mmol, 1 eq, M.W. 1800: 41.9 mmol, 1 eq) of the polyethyleneimine were placed in the flask and 9.73 mL (120 mmol: M.W. 600: 40 eq and M.W. 1800 120 eq) formaldehyde solution and 4.53 mL (120 mmol: M.W. 600: 40 eq and M.W. 1800 120 eq) formic acid were added. The flask was equipped with a condenser and the reaction mixture was heated to 60° C. for 16 hour with an oil bath. After 16 hour the mixture was allowed to cool to room temperature and the solvents were removed under reduced pressure. Then, the crude product was dissolved in 20 mL EtOH anhydrous and 4 g of Amberlite resin was added to the solution. The resulting mixture was stirred for 4 hour or for 16 hour at room temperature before the resin was filtered of and the EtOH was removed under reduced pressure. The methylated polymer was obtained as a dark yellow oil (1.8 g from the M.W. 600 sample and 1.7 g from the M.W. 1800 sample).

For the sample using polyethyleneimine M.W. 10,000: A 250 mL round bottom flask was equipped with a 2 cm teflon stirring bar and placed over a magnetic stirring plate. 1.8 g (41.9 mmol, 1 eq) of the polyethyleneimine were placed in the flask and 9.73 mL (120 mmol, 120 eq) formaldehyde solution and 4.53 mL (120 mmol, 120 eq) formic acid were added. The flask was equipped with a condenser and the reaction mixture was heated to 60° C. for 16 hour with an oil bath. After 16 hour the mixture was allowed to cool to room temperature and the solvents were removed under reduced pressure. Then, the crude product was dissolved in 20 mL EtOH anhydrous and 4 g of Amberlite resin was added to the solution. The resulting mixture was stirred for 16 hour at room temperature before the resin was filtered of and the EtOH was removed under reduced pressure. The resulting crude product was dissolved in 10 mL CH₂Cl₂ and 10 mL of a 2 M aqueous solution of NaOH in water. The phases were separated and the aqueous layer was extracted three times with 10 mL of CH₂Cl₂. The organic phases were dried over MgSO₄ and the CH₂Cl₂ was removed under reduced pressure to yield the methylated polyethyleneimine as a yellow oil.

Methylated polyethyleneimine (M.W. 600 before methylation):

¹H NMR (CDCl₃, 400 MHz): δ=2.18-2.91 (m), no NH signal appear in the spectra

¹³C NMR (CDCl₃, 100.7 MHz): δ=42.2 (q), 44.1 (q), 44.4 (q), 50.5-56.0 (m, t)

Methylated polyethyleneimine (M.W. 1800 before methylation)

¹H NMR (CDCl₃, 400 MHz): δ=2.16 (s, CH₃), 2.23 (bs, CH₃), 2.44-2.64 (m), no NH signal appear in the spectra

¹³C NMR (CDCl₃, 100.7 MHz): δ=41.5 (q), 44.0 (q), 50.8-51.1 (m, t), 53.7 (t), 55.0 (t)

Methylated polyethyleneimine (M.W. 1800 before methylation)

¹H NMR (CDCl₃, 400 MHz): δ=2.18 (s, CH₃), 2.21 (s, CH₃), 2.28-2.62 (m), no NH signal appear in the spectra.

¹³C NMR (CDCl₃, 100.7 MHz): δ=42.9 (q), 43.0 (q), 45.9 (q), 46.0 (q), 52.8-54.0 (m, t), 55.8-56.9 (m, t), 57.2-57.8 (m, t)

Example 16B: Use of the Polyamine to Expel Acetonitrile from Water

The methylated polyamines were investigated as additives for switchable ionic strength solutions. To measure the extent of acetonitrile being forced out of an aqueous phase by an increase in ionic strength, and the amounts of amine, which remained in the aqueous phase, 1:1 w/w solutions of acetonitrile and water (1.5 g each) were prepared in graduated cylinders. 300 mg of the non-ionic polyamine additive were added and the cylinders were capped with rubber septa. After 30 min of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle at room temperature, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in D₂O in NMR tubes. A known amount of ethyl acetate or dimethylformamide (DMF) was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired and through integration of the ethyl acetate or DMF standard, a concentration of acetonitrile or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase giving a percentage of the compound being forced out. The results are shown in the following table.

polyethyleneimine Acetonitrile forced out M.W. 600 56% M.W. 1800 72% M.W. 10000 77%

99.9% of the polyamine was retained in the aqueous phase.

Argon was then bubbled through the solution while heating to 50° C. until the two phases recombined into a single phase (typically 30 min). Bubbling CO₂ through the mixture again for 30 min caused the liquid mixture to split into two phases and a subsequent bubbling of argon for 30 min caused the two phases to merge again, which shows that the process was fully reversible.

Example 17: Preparation and Use of a Tetraamine for Expulsion of THF from Water Example 17A: Preparation of the Tetraamine

Spermine (97% purity) was purchased from Alfa Aesar, formaldehyde (37% in H₂O), Zn powder from Sigma-Aldrich and acetic acid from Fisher Scientific.

A 250 mL round bottom flask was equipped with a 2 cm teflon stirring bar and placed over a magnetic stirring plate. 2.02 g (10 mmol, 1.0 eq) spermine were placed in the flask and dissolved in 40 mL water. Afterwards, 9.72 mL (120 mmol, 12.0 eq) formaldehyde solution and 13.7 mL (240 mmol, 24.0 eq) acetic acid were added and the solution was allowed to stir at room temperature for 15 min. Afterwards, 7.84 g (120 mmol, 12.0 eq) Zn powder were added in small portions, which resulted in gas formation. A cold water bath was used to maintain the temperature in the flask under 40° C. After complete addition the reaction mixture was vigorously stirred for 16 hour at room temperature. 20 mL NH₃-solution were added and the aqueous phase was extracted with ethyl acetate in a separation funnel (3×25 mL).

The combined organic layers were dried over MgSO₄, filtered through filter paper removed under reduced pressure. The crude product was purified by high vacuum distillation to yield 1.3 g (4.5 mmol, 42%) of a yellow oil which was formally called N¹,N^(1′)-(butane-1,4-diyl)bis(N¹,N³,N³-trimethylpropane-1,3-diamine). As used herein, this compound is referred to as MeSpe (i.e. methylated spermine).

¹H NMR (CDCl₃, 400 MHz): δ=1.36-1.44 (m, 4H, CH₂), 1.55-1.66 (m, 4H, CH₂), 2.18 (s, 6H, CH₃), 2.19 (s, 12H, CH₃), 2.21-2.27 (m, 4H, CH₂), 2.28-2.35 (m, 8H, CH₂);

¹³C NMR (CDCl₃, 100.7 MHz): δ=25.3 (t), 25.7 (t), 42.3 (q), 45.6 (q), 55.8 (t), 57.8 (t), 58.0 (t);

MS (EI): m/z (%)=287.32 (7), 286.31 (41) [M]⁺, 98.08 (28), 86.08 (44), 85.07 (100), 84.07 (41);

HRMS (EI): calc. for [M]⁺: 286.3097, found: 286.3091.

Example 17B: Reversible Solvent Switching of Tetraamine/Water System

The methylated spermine was investigated as an additive for switchable ionic strength solutions. To measure the extent of THF being forced out of an aqueous phase by an increase in ionic strength, and the amounts of amine, which remained in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. The appropriate mass of amine additive to result in a 0.80 molal solution was added and the cylinders were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in d₃-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired and through integration of the ethyl acetate standard, a concentration of THF or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase giving a percentage of the compound being forced out or retained. Then argon was bubbled through the solution while heating to 50° C. until the two phases recombined (15 to 60 min). The whole switching process (30 min CO₂, sample take, then another 30 min of Ar) was repeated. The results are shown in the following table.

Salting Out-Experiments Using Methylated Spermine (MeSpe).

run THF forced out Additive retained in THF 1 84.3% 99.85% 2 85.5% 99.79%

Example 17C: NMR Measurement of the Degree of Protonation of Methylated Spermine by Carbonated Water

The degree of protonation of the tetraamine (methylated spermine) upon contact with a carbon dioxide trigger was investigated by ¹H NMR.

In order to establish the chemical shifts of the protonated bases, molar equivalents of several strong acids, including HCl and HNO₃, were added to separate solutions of the tetraamine dissolved in D₂O. ¹H NMR spectra were acquired on a Bruker AV-400 NMR spectrometer at 400.3 MHz for three replicate solutions of the amine. An average value of each chemical shift for each protonated base was calculated along with standard deviations. If the base when reacted with the trigger to ionic salt form showed chemical shifts within this error range, it was considered to be 100% protonated within experimental error. The ¹H NMR chemical shifts of the unprotonated amine were also measured.

The extent of protonation of the additive at room temperature at 0.1 M (in D₂O) was monitored by ¹H NMR. The amine was dissolved in D₂O in an NMR tube and sealed with a rubber septa. The spectrum was then acquired. Subsequently, two narrow gauge steel needles were inserted and gas was gently bubbled through one of them into the solution at approximately 4-5 bubbles per second. The second needle served as a vent for the gaseous phase.

Firstly CO₂ was bubbled through the solution for the required length of time and then the spectrum was re-acquired. This process was repeated. The % protonation of the amine was determined from the observed chemical shifts by determining the amount of movement of the peaks from the normal position for the unprotonated amine towards the position expected for the fully protonated amine.

The results show that the tetramine was protonated to a degree of 93%.

Example 18: Osmotic Desalination System

Water desalination by reverse osmosis is energetically costly. An alternative that has been proposed in the literature is forward osmosis (FIG. 18), where water flows across a membrane from seawater into a concentrated ammonium carbonate solution (the “draw solution”). Once the flow is complete, the draw solution is removed from the system and heated to eliminate the NH₃ and CO₂. The principle costs of the process are the energy input during the heating step and the supply of make-up ammonium carbonate. The limiting factors for the technology are, according to a 2006 review of the field (Cath, T. Y.; Childress, A. E.; Elimelech, M. J. Membrane Sci. 2006, 281, 70-87). a “lack of high-performance membranes and the necessity for an easily separable draw solution.”

Described in this example is a new easily separable draw solution, which takes advantage of the present method of reversibly converting a switchable water from low to high ionic strength. The osmotic pressure of a switchable water should dramatically rise as the conversion from low ionic strength to high ionic strength takes place. Although the osmotic pressures of the solution before and after CO₂ have not been measured, literature data (Cath, T. Y.; Childress, A. E.; Elimelech, M. J. Membrane Sci. 2006, 281, 70-87) show that the osmotic pressure of a 4 M solution of a neutral organic such as sucrose is much lower (about 130 atm) than the osmotic pressure of a salt containing a dication such as MgCl₂ (800 atm). This reversible change in osmotic pressure can be used in a method for desalination of water as depicted in FIG. 19.

The process depicted in FIG. 19 employs a switchable water solution in its ionic form as the draw solution. After forward osmosis, the seawater is removed and the CO₂ is removed from the switchable water solution, dropping the osmotic pressure dramatically. Reverse osmosis produces fresh water from the switchable water solution with little energy requirement because of the low osmotic pressure.

The key advantages of this process over conventional forward osmosis are the expected lower energy requirement for the heating step (see Table of expected energy requirements below) and the facile and complete recycling of the amine. The key advantage of the proposed process over conventional reverse osmosis is the much lower pressure requirement during the reverse osmosis step.

Energy requirement Energy requirement for process with for proposed Process step NH₄CO₃, kJ/mol process, kJ/mol Deprotonation of NH₄ ⁺ or 52.3³ 36.9³ NR₃H⁺ Removal of CO₂ from 19.4 19.4 water Removal of NH₃ from 30.5 0 water Reverse osmosis step 0 unknown TOTAL 102.2 >56.3 ³Mucci, A.; Domain, R.; Benoit, R. L. Can. J. Chem. 1980, 58, 953-958.

A modification of this process, shown in FIG. 20, differs only in the last step, where the switchable water additive in the solution is switched “off”, or back to its nonionic form, and then removed by a method other than reverse osmosis. For example, if the non-ionic form of the additive is insoluble or immiscible with water, then it can be removed by filtration or decantation, with any small amounts of remaining additive in the water being removed by passing the water through silica. Results have shown successful use of such a separation process.

Sodium chloride was purchased from EMD Chemicals (Gibbstown, N.J., USA) while bone dry grade carbon dioxide was purchased from Air Liquide (Toronto, ON, Canada). The Seapack Emergency Desalinator bag was purchased from Hydration Technology Innovations (Scottsdale, Ariz., USA). Ultra pure water (18 MΩ) was obtained using an Elga Lab Water PureLab Flex system (High Wycombe, UK). Reverse Osmosis (RO) experiments were conducted using a Sterlitech HP4750 Stirred cell with two different Sterlitech ultra filtration membranes (TF UF GM membrane PN: YMGMSP3301 and Koch Flat sheet membrane HFK 131 PN: YMHFK13118).

Example 18A: Forward and Reverse Osmosis Experiments with 1% Salt Water Using MW=35 k Functionalized PMMA

A solution of 15 g of 3-(dimethylamino)-1-propylamine functionalized polymethyl methacrylate (MW=35,000) in 85 mL deionized water was added to the inner membrane nutrient delivery spout (green capped) of the desalination bag. Carbon dioxide was introduced to the same solution directly in the bag via a glass dispersion tube at a pressure of 10 psi. Bubbling was continued for 45 minutes. A solution of 1 weight % sodium chloride in water (1050 mL) was added to the sample port (red capped) of the desalination bag typically used for introduction of seawater. The bag was left at room temperature for 6 hours and then the polymer solution was poured out via the green capped spout. The volume of solution was approximately 145 mL and the solution was returned to the bag via the same spout. An additional 15 g of solid polymer was added via the same spout along with an additional 15 mL of water. The bag was agitated for approximately 10 minutes by hand and then carbon dioxide was bubbled through polymer solution for 1 hour and rinsed with an additional 15 mL of water. The bag was left for 16 hours at room temperature followed by measuring the volume of polymer solution which was found to be approximately 370 mL. The solution was then heated to 75° C. for 5 hours in a glass media jar until no evolution of gas bubbles was observed indicating solution was “switched off”.

The stirred cell was equipped with a membrane and 100 mL of the 3-(dimethylamino)-1-propylamine functionalized PMMA aqueous solution was added. The cell was closed and pressurized with argon. The table shows the use of two different membranes and pressures and flux needed for each experiments.

Polymer solution Membrane Pressure Flux (ml/min) PMMA 35,000 TF UF GM 67 bar 0.167 PMMA 35,000 HFK 131 40 bar 0.075

Example 18B: Forward and Reverse Osmosis Experiments with 1% Salt Water Using MW=15 k Functionalized PMMA

A solution of 15 g of 3-(dimethylamino)-1-propylamine functionalized polymethyl methacrylate (MW=15,000) in 100 mL deionized water was added to the inner membrane nutrient delivery spout (green capped) of the desalination bag. A solution of 1 weight % sodium chloride in water (1050 mL) was added to the sample port (red capped) of the desalination bag typically used for introduction of seawater. The bag was left at room temperature overnight without carbonating and then the polymer solution was poured out via the green capped spout. The volume of the solution was approximately 115 mL, which was unchanged since the polymer solution was not “switched on” by carbon dioxide. The solution was returned to the bag via the same spout and carbonated directly by bubbling with carbon dioxide using gas dispersion tube at 10 psi for 45 minutes. The bag was left for 16 hours at room temperature followed by measuring the volume of polymer solution which was found to be approximately 250 mL. This solution was again carbonated directly by bubbling with carbon dioxide using a gas dispersion tube at 10 psi for 5 minutes, and 100 mL of it was set aside for reverse osmosis experiment in “switched on” form. Remaining solution was heated to 70° C. for 2 hours in a glass media jar until no evolution of gas bubbles was observed indicating solution was “switched off”.

Reverse Osmosis in Switched on Form

The stirred cell was equipped with a membrane and above 100 mL of 3-(dimethylamino)-1-propylamine functionalized PMMA aqueous solution was added without previously removing the CO₂. The cell was closed and pressurized with argon. The table shows the use of two different membranes and pressures and flux needed for each experiment.

Polymer solution Membrane Pressure Flux (ml/min) PMMA 15,000 (“ON”) TF UF GM 40 bar 0.30 PMMA 15,000 (“ON”) HFK 131 40 bar 0.20

Reverse Osmosis in Switched Off Form

The stirred cell was equipped with a membrane and 100 mL of 3-(dimethylamino)-1-propylamine functionalized PMMA aqueous solution was added in the deactivated form. The cell was closed and pressurized with argon. The table shows the use of two different membranes and pressures and flux needed for each experiment.

Polymer solution Membrane Pressure Flux (ml/min) PMMA 15,000 (“OFF”) TF UF GM 40 bar 0.20 PMMA 15,000 (“OFF”) HFK 131 40 bar 0.28

Forward Osmosis Using DMCA as Draw Solution

A draw solution of 127.0 mL (108.0 g, 0.85 mol) dimethylcyclohexylamine in 127.0 mL deionized water was prepared. It was carbonated by bubbling with carbon dioxide using a gas dispersion tube at 1 atm for 1.5 h until all of the amine disappeared and added to the inner membrane nutrient delivery spout (green capped) of the desalination bag. A solution of 1 weight % sodium chloride in water (1.0 L) was added to the sample port (red capped) of the desalination bag typically used for introduction of seawater. After 5 h the draw solution was removed from the pack and the volume measured (900 mL), while the volume of the NaCl feeding solution decreased to 350 mL. Due to the low concentration of DMCA in water and incomplete conversion of the salt, it was not possible to force the DMCA out of the water.

Example 19: Preparation and Use of a Diamidine for Expulsion of THF from Water Example 19A: Preparation of the Diamidine

1,4-Diaminobutane was purchased from Sigma-Aldrich and dimethylacetamide dimethylacetale was purchased from TCI.

A 100 mL flask was equipped with a condenser and a 1 cm stirring bar and was then placed over a stirplate. 1.14 mL (1.0 g, 11.3 mmol, 1 eq.) of 1,4-diaminobutane and 3.64 mL (3.31 g, 24.9 mmol, 2.2 eq.) of dimethylacetamide dimethylacetate were the placed into the flask. The reaction mixture was then stirred with 600 rpm and heated to 60° C. After 2 h the reaction mixture was allowed to cool to room temperature and the resulting methanol was removed under reduced pressure to yield a yellow oil. This crude product was then purified by high vacuum distillation. The pure product was obtained as a light yellow oil (2.32 g, 10.2 mmol, 91%). The compound was called N′,N″-(butane-1,4-diyl)bis(N,N-dimethylacetimidamide) and in this application is referred to as “DIAC” (i.e. diacetamidine)

¹H NMR (CDCl₃, 400 MHz): δ=1.45-1.53 (m, 4H, CH₂), 1.80 (s, 3H, CON, 2.79 (s, 6H, N(CH₃)₂), 3.09-3.19 (m, 4H, CH₂);

¹³C NMR (CDCl₃, 100.7 MHz): δ=12.3 (q, CCH₃), 30.2 (t, CH₂), 37.9 (q, 2C, N(CH₃)₂), 50.0 (t, CH₂), 158.7 (s);

MS (EI): m/z (%)=227.22 (3), 226.21 (21), 198.16 (7), 182.17 (7), 141.14 (14), 140.13 (21), 128.11 (10), 127.10 (30), 114.11 (23), 113.11 (28), 112.09 (52), 99.09 (27), 70.07 (45), 56.05 (100);

HRMS (EI): calc. for [M]⁺: 226.2157, found: 226.2161.

Example 19B: Reversible Solvent Switching of Diamidine/Water System

The diamidine was investigated as additive for switchable ionic strength solutions. To measure the extent of THF being forced out of an aqueous phase by an increase in ionic strength, and the amounts of amine, which remained in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. The appropriate mass of amine additive to result in a 0.80 molal solution was added and the cylinders were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in d₃-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired and through integration of the ethyl acetate standard, a concentration of THF or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase giving a percentage of the compound being forced out or retained. The results showed that the amount of THF forced out of the aqueous phase was 54.5% and the amount of additive retained in the aqueous phase was 99.5%

Then argon was bubbled through the solution while heating to 50° C. until the two phases recombined (15 to 60 min).

Example 20: Precipitation of an Organic Solid Using Switchable Water

Ten milliliters of water was pipetted into a glass centrifuge tube along with 2.038 g TMDAB (˜5:1 w/w solution). 68.2 mg of (+)-camphor (used as is from Sigma-Aldrich) was added to the solution. The solution was heated in a 70° C. water bath to expedite the dissolution of the camphor. After complete dissolution of the solid (camphor) and cooling to room temperature (23° C.), the solid remained dissolved in the aqueous solution.

The centrifuge tube was capped with a rubber septum. CO₂ was introduced into the solution via a single narrow gauge steel needle at a flow rate of about 5 mL min⁻¹. A second needle was inserted into the tube, but not into the solution, to act as a gas outlet. After 30 minutes of bubbling CO₂ through the solution a white precipitate appeared throughout the aqueous solution.

The solution was centrifuged for 5 minutes, using a Fisher Scientific Centrific 228 centrifuge at a speed of 3300 RPM, such that all the white solids collected at the top of the aqueous solution. The white solids were collected by vacuum filtration and weighed on a Mettler-Toledo AG245 analytical balance. A mass of 24.0 mg was obtained, resulting in a 35.2% recovery of the original dissolved solid.

Example 21: Primary Amines as Switchable Additives

Primary amines were tested as switchable water additives. The switching of the non-ionized form to the charged form (which is probably a mixture of bicarbonate and carbamate salts) proceeded well. The separation of an organic liquid was observed. However, conversion of the ionic form back to the non-ionized form was unsuccessful. Primary amines are therefore only useful as additives in applications where a single switch to the ionic form, without conversion back to the non-ionized form, is sufficient. Thus, primary amine additives are not reversibly “switchable”.

Example 21A: Ethanolamine (5:5:1)

In a glass vial, 5.018 g H₂O, 1.006 g ethanolamine, and 4.998 g THF were mixed to generate a single phase, clear, colourless solution. A stir bar was added to the vial and the vial was capped with a rubber septa. CO₂ was introduced into the solution via a single narrow gauge steel needle at a flow rate of about 5 mL min⁻¹. A second needle was inserted through the septa, but not into the solution, to act as a gas outlet. CO₂ was bubbled through the solution for 20 minutes until two liquid phases (aqueous and organic) were observed. It was found by ¹H NMR spectroscopy that ˜62% of the THF was forced out of the aqueous phase into the new organic phase.

The two phase mixture was then placed in a 60° C. water bath while N₂ was bubbled through the mixture in a fashion similar to the previous bubbling of CO₂. This was performed for 60 minutes. Although some THF boiled off, the two phases did not recombine. The temperature was increased to 75° C. for 30 minutes which appeared to boil off the remainder of the THF as the volume returned to that of the water and amine mixture. Some ethanolamine may have boiled off as well. At this point, a single liquid phase was observed, as the THF was boiled off, however, the phase was cloudy and it appeared to have a white precipitate (likely carbamate salts).

The temperature of the water bath was then increased to 85° C. and N₂ bubbling was continued for 90 minutes, giving a total N₂ treatment of 3 hours. No additional physical changes were observed. The solution remained cloudy white in colour and some of the white precipitate had collected on the sides of the vial.

Example 21B: Ethylenediamine (18:18:1)

In a glass vial, 5.004 g H₂O, 0.283 g ethylenediamine, and 5.033 g THF were mixed to generate a single phase, clear, colourless solution. A stir bar was added to the vial and the vial was capped with a rubber septa. CO₂ was introduced into the solution via a single narrow gauge steel needle at a flow rate of about 5 mL min⁻¹. A second needle was inserted through the septa, but not into the solution, to act as a gas outlet. CO₂ was bubbled through the solution for 10 minutes until two liquid phases (aqueous and organic) were observed. It was found by ¹H NMR that ˜67% of the THF was forced out of the aqueous phase into the new organic phase.

The two phase mixture was then placed in a 60° C. water bath while N₂ was bubbled through the mixture in a fashion similar to the previous bubbling of CO₂. This was performed for 60 minutes where some THF evaporated, but the two phases did not recombine. The temperature of the water bath was then increased to 85° C. and N₂ bubbling was continued for 120 minutes, giving a total N₂ treatment of 3 hours. It appeared that all of the THF had evaporated as the volume had returned to that of the water and amine mixture. The solution was a single yellow liquid phase at this point, however a white precipitate (likely carbamate salts) caused the solution to appear cloudy.

Example 22: Salting Out THF from Water Using Secondary Amine Switchable Additives

In general, from the observations using primary amines, secondary amines were expected to be difficult to reverse, because both secondary and primary amines tend to form carbamate salts in addition to bicarbonate salts when their aqueous solutions are contacted with CO₂. However the following secondary amines were found to be reversibly switchable. Without wishing to be bound by theory, it is possible that the reversibility results from a tendency to form more bicarbonate than carbamate salts.

The N-tert-butylethanolamine was purchased from TCI America and N-tert-butymethylamine was purchased from Sigma-Aldrich. Both compounds were used without further purification.

N-tert-Butylethanolamine and N-tert-butymethylamine were investigated as additives for switchable ionic strength solutions. To measure the extent of THF being forced out of an aqueous phase by an increase in ionic strength, and to measure the amount of amine remaining in the aqueous phase, 1:1 w/w solutions of THF and water (1.5 g each) were prepared in graduated cylinders. The appropriate mass of amine additive to result in a 1.60 molal solution was added and the cylinders were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in d₃-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired and through integration of the ethyl acetate standard, a concentration of THF or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase giving a percentage of the compound being forced out or retained. Then argon was bubbled through the solution at 5 mL/min while heating to 50° C. until the two phases recombined (30 min for N-tert-butylethanolamine). The recombining of the phases when N-tert-butylmethylamine was used as an additive was not successful at 30 min but was achieved after 2 hours at a higher Ar flow rate of 15 mL/min. THF was added afterwards to replace the amount of THF being evaporated during the procedure. The whole switching process (30 min CO₂, sample take, then another Ar treatment) was repeated. The results are shown in the following table.

Salting Out-Experiments Using Secondary Amine Additives.

Amine THF forced out Additive retained in H2O N-tert-butylethanolamine 68.7 ± 0.4% 99.84 ± 0.04% N-tert-butymethylamine 67.6 ± 0.8% 99.75 ± 0.04%

Example 23: Synthesis of Polymeric Switchable Water Additives

Polyethyleneimines (“PEIs”, MW=600, 99%; 1,800, 99%; 10,000, 99%) were purchased from Alfa Aesar. Iodoethane, 99%, Iodopropane, 99% Iodobutane, 99% and K₂CO₃ were purchased from Sigma-Aldrich. NaOH was purchased from Acros. EtOH was purchased from Greenfield Alcohols. Ethyl acetate and MgSO₄ were purchased from Fisher. All reagents were used without further purification. A 15% (w/v) NaOH solution was made by dissolving 15 g of NaOH in 100 mL deionized water.

General procedure I (GP I) for the alkylation of PEIs: In a round bottom flask, equipped with a magnetic stir-bar, iodoalkane was dissolved in absolute EtOH and stirred at 600 rpm. To this, a solution of PEI in EtOH and solid K₂CO₃ were added. The round bottom flask was then equipped with a reflux condenser and the reaction mixture was heated to reflux (80° C.) for 3 days. After cooling to room temperature, the K₂CO₃ was filtered off and the EtOH was removed under reduced pressure. The crude product was then dissolved in a mixture of EtOAc and 15% (w/v) NaOH solution in water. The phases were separated and the organic layer was washed twice with 15% (w/v) NaOH solution in water. The organic layer was then dried with MgSO₄ and removed under reduced pressure to yield yellow oils.

General procedure II (GP II) for the alkylation of PEIs: In a round bottom flask, equipped with a magnetic stir-bar, iodoalkane was dissolved in absolute EtOH and stirred at 600 rpm. To this, a solution of PEI in EtOH and solid K₂CO₃ were added. The round bottom flask was then equipped with a reflux condenser and the reaction mixture was heated to reflux (80° C.) for 3 days. After cooling to room temperature, another portion of K₂CO₃ was added and the mixture was refluxed again for 3 d. After cooling to r.t., the K₂CO₃ was filtered off and the EtOH was removed under reduced pressure. The crude product was then dissolved in a mixture of EtOAc and 15% (w/v) NaOH solution in water. The phases were separated and the organic layer was washed twice with 15% (w/v) NaOH solution in water. The organic layer was then dried with MgSO₄ and removed under reduced pressure to yield yellow oils.

23.1.1 Synthesis of Ethylated Polyethyleneimines (EPEI)

23.1.1.1 Ethylated Polyethyleneimine (EPEI) MW=600

According to GP I, 3.1 mL (6.1 g, 39.0 mmol) iodoethane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=600) in 10 mL EtOH in the presence of 8.3 g (60.0 mmol) K₂CO₃. Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 1.84 g (65%) of a light yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.969 (bt, 3H, CH₃), 2.39-2.56 (m, 6H, CH₂);

¹³C NMR (CDCl₃, 100.7 MHz): δ=11.8 (CH₃), 47.4 (CH₂ ethyl), 48.6 (CH₂ ethylene), 50.9-54.0 (CH₂ ethylene);

NMR spectrum shows 9% quaternized nitrogens in the polymer.

IR (film): {tilde over (υ)} [cm⁻¹]=2967 (s), 2934 (m), 2808 (s), 1653 (w), 1457 (m), 1382 (w), 1292 (w), 1097 (w), 1062 (m).

23.1.1.2 Ethylated Polyethyleneimine (EPEI) MW=1,800

According to GP I, 3.1 mL (6.1 g, 39.0 mmol) iodoethane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=1,800) in 10 mL EtOH in the presence of 8.3 g (60.0 mmol) K₂CO₃. Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 2.38 g (84%) of a light brown oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.91 (bt, 3H, CH₃), 2.38-2.54 (m, 6H, CH₂);

¹³C NMR (CDCl₃, 100.7 MHz): δ=11.8 (CH₃), 47.5 (CH₂ ethyl), 50.8-54.1 (CH₂ backbone);

IR (film): {tilde over (υ)} [cm⁻¹]=2966 (s), 2933 (m), 2807 (s), 1456 (m), 1382 (w), 1292 (w), 1097 (w), 1061 (m).

23.1.1.3 Ethylated Polyethyleneimine (EPEI) MW=10,000

According to GP I, 3.1 mL (6.1 g, 39.0 mmol) iodoethane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=10,000) in 10 mL EtOH in the presence of 8.3 g (60.0 mmol) K₂CO₃. Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 2.23 g (78%) of a light yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.98 (bt, 3H, CH₃), 1.40 (bs, remaining free NH), 2.42-2.62 (m, 6H, CH₂);

NMR spectrum shows 7% quaternized nitrogens in the polymer.

¹³C NMR (CDCl₃, 100.7 MHz): δ=11.7 (CH₃), 47.4 (CH₂ ethyl), 47.8-54.0 (CH₂ backbone);

IR (film): {tilde over (υ)} [cm⁻¹]=2973 (s), 2809 (s), 1643 (w), 1562 (w), 1471 (m), 1100 (w), 1055 (w).

23.1.2 Synthesis of Propylated Polyethyleneimines (PPEI)

23.1.2.1 Propylated Polyethyleneimine (PPEI) MW=600

According to GP II, 4.7 mL (8.2 g, 48.0 mmol) iodopropane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=600) in 10 mL EtOH in the presence of 21.6 g (156.0 mmol) K₂CO₃ (over two equal additions). Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 2.54 g (71%) of a yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.84 (bt, 3H, CH₃), 1.41 (bq, 2H, CH₂, propyl), 2.30-2.39 (m, 2H, CH₂, propyl), 2.43-2.57 (m, 4H, CH₂, backbone);

NMR spectrum shows 6% quaternized nitrogens in the polymer.

¹³C NMR (CDCl₃, 100.7 MHz): δ=11.4 (CH₃), 20.4 (CH₂, propyl), 52.2-53.9 (CH₂ backbone) 56.9 (CH₂, propyl);

IR (film): {tilde over (υ)} [cm⁻¹]=2957 (s), 2933 (m), 2807 (s), 1458 (m), 1378 (w), 1261 (w), 1076 (w), 800 (m).

23.1.2.2 Propylated Polyethyleneimine (PPEI) MW=1,800

According to GP II, 4.7 mL (8.2 g, 48.0 mmol) iodopropane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=1,800) in 10 mL EtOH in the presence of 21.6 g (156.0 mmol) K₂CO₃ (over two equal additions). Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 2.3 g (65%) of a yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.83 (bt, 3H, CH₃), 1.41 (bq, 2H, CH₂, propyl), 1.76 (bs, remaining free NH), 2.35 (bq, 2H, CH₂, propyl), 2.42-2.58 (m, 4H, CH₂, backbone);

NMR spectrum shows 12% quaternized nitrogens in the polymer.

¹³C NMR (CDCl₃, 100.7 MHz): δ=12.1 (CH₃), 20.3 (CH₂, propyl), 52.3-53.9 (CH₂ backbone) 56.8 (CH₂, propyl);

IR (film): {tilde over (υ)} [cm⁻¹]=3421 (s), 2958 (s), 2872 (m), 2809 (s), 1653 (m), 2559 (m), 1464 (m), 1379 (w), 1076 (w), 800 (m).

23.1.2.3 Propylated Polyethyleneimine (PPEI) MW=10,000

According to GP II, 5.7 mL (10.0 g, 5870 mmol) iodopropane in 12 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=10,000) in 12 mL EtOH in the presence of 26.2 g (190.0 mmol) K₂CO₃ (over two equal additions). Work-up with NaOH (3×12 mL) and EtOAc (12 mL) yielded 4.2 g (99%) of a yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.82 (bt, 3H, CH₃), 1.40 (bq, 2H, CH₂, propyl), 1.76 (bs, remaining free NH), 2.34 (bq, 2H, CH₂, propyl), 2.42-2.58 (m, 4H, CH₂, backbone);

NMR spectrum shows 15% quaternized nitrogens in the polymer.

¹³C NMR (CDCl₃, 100.7 MHz): δ=11.8 (CH₃), 20.4 (CH₂, propyl), 52.2-53.9 (CH₂ backbone) 56.8 (CH₂, propyl);

IR (film): {tilde over (υ)} [cm⁻¹]=3439 (m), 2958 (s), 2933 (m), 2872 (s), 2808 (s), 1463 (m), 1379 (w), 1075 (w).

23.1.3 Synthesis of Butylated Polyethyleneimines (BPEI)

23.1.3.1 Butylated Polyethyleneimine (BPEI) MW=600

According to GP II, 5.46 mL (8.83 g, 48.0 mmol) iodobutane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=600) in 10 mL EtOH in the presence of 21.6 g (156.0 mmol) K₂CO₃ (over two equal additions). Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 3.95 g (98%) of a yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.86 (bt, 3H, CH₃), 1.19-1.30 (m, 2H, CH₂ butyl), 1.31-1.42 (m, 2H, CH₂ butyl), 2.32-2.42 (m, 2H, CH₂ butyl), 2.44-2.54 (m, CH₂ ethylene);

¹³C NMR (CDCl₃, 100.7 MHz): δ=14.1 (CH₃), 20.7 (CH₂ butyl), 29.4 (CH₂ butyl), 52.4-54.1 (CH₂, ethylene) 54.5 (CH₂ butyl), 54.8-55.1 (CH₂ ethylene);

IR (film): {tilde over (υ)} [cm⁻¹]=2956 (s), 2931 (s), 2861 (m), 2805 (s), 1458 (m), 1376 (w), 1083 (m).

23.1.3.2 Butylated Polyethyleneimine (BPEI) MW=1,800

According to GP II, 5.46 mL (8.83 g, 48.0 mmol) iodobutane in 10 mL EtOH was reacted with 1.8 g (41.9 mmol) polyethyleneimine (MW=1,800) in 10 mL EtOH in the presence of 21.6 g (156.0 mmol) K₂CO₃ (over two equal additions). Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 2.50 g (62%) of a yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.86 (bt, 3H, CH₃), 1.24 (bq, 2H, CH₂ butyl), 1.31-1.44 (m, 2H, CH₂ butyl), 1.64 (bs, remaining NH), 2.37 (q, 2H, CH₂ butyl), 2.42-2.54 (m, CH₂ ethylene), NMR spectrum shows 14% quaternized nitrogens in the polymer;

¹³C NMR (CDCl₃, 100.7 MHz): δ=14.1 (CH₃), 20.7 (CH₂ butyl), 29.4 (CH₂ butyl), 52.1-53.8 (CH₂, ethylene) 54.5 (CH₂ butyl), 58.0-59.2 (CH₂ ethylene);

IR (film): {tilde over (υ)} [cm⁻¹]=3424, (s), 2957 (s), 2871 (m), 2810 (s), 1647 (s), 1558 (w), 1458 (m).

23.1.3.3 Butylated Polyethyleneimine (BPEI) MW=10,000

According to GP II, 5.46 mL (8.83 g, 48.0 mmol) iodobutane in 10 mL EtOH was reacted with 2.0 g (46.5 mmol) polyethyleneimine (MW=10,000) in 10 mL EtOH in the presence of 21.2 g (154.0 mmol) K₂CO₃ (over two equal additions). Work-up with NaOH (3×10 mL) and EtOAc (10 mL) yielded 2.47 g (55%) of a yellow oil.

¹H NMR (CDCl₃, 400 MHz): δ=0.88 (bt, 3H, CH₃), 1.27 (bq, 2H, CH₂ butyl), 1.33-1.44 (m, 2H, CH₂ butyl), 2.32-2.43 (m, 2H, CH₂ butyl), 2.44-2.56 (m, CH₂ ethylene);

NMR spectrum shows 3% quaternized nitrogens in the polymer.

¹³C NMR (CDCl₃, 100.7 MHz): δ=14.1 (CH₃), 20.7 (CH₂ butyl), 29.5 (CH₂ butyl), 52.0-53.5 (CH₂, ethylene) 54.5 (CH₂ butyl), 54.8-55.1 (CH₂ ethylene);

IR (film): {tilde over (υ)} [cm⁻¹]=2955 (s), 2930 (s), 2861 (m), 2805 (s), 1467 (m), 1378 (w), 1080 (m).

23.2 Polydiallylmethylamine (MW=5,000)

Polydiallylmethylamine hydrochloride MW=5,000 (25% solids in water) was purchased from Polysciences, Inc. NaOH was purchased from Acros Organics. Dichloromethane and MgSO₄ were purchased from Fisher. A 15% (w/v) solution was made by dissolving 15 g of NaOH in 100 mL deionized water.

4.0 g of Polydiallylmethylamine hydrochloride MW=5000 (25% solids in water) was placed into a 50 mL round-bottom flask equipped with a 1 cm magnetic stir-bar. 10 mL of dichloromethane was added and the mixture was stirred at 600 rpm. Then 10 mL of 15% (w/v) NaOH solution was slowly added and the stirring was continued for 1 hour after complete addition. The mixture was then transferred into a 100 mL separation funnel and the phases were separated. The organic layer was then washed twice with 5 mL of a 15% (w/v) NaOH solution, dried over MgSO₄ and removed under reduced pressure. 0.5 g (69%) of the polydiallylmethylamine was obtained as a yellow solid.

23.3 Polymethyl Methacrylate (PMMA) Based Materials

All reactions were conducted in air unless stated otherwise. NMR spectra were recorded on a Varian 400-MR NMR spectrometer (Agilent, Mississauga, Ontario, Canada). All NMR spectra are referenced against residual protonated solvent.

All chemicals listed below were used as received. Polymethyl methacrylate (MW=15,000 and MW=35,000) was purchased from Acros Organics (Fisher Scientific, Ottawa, Ontario, Canada). Polymethyl methacrylate (MW=120,000), and 3-dimethylamino-1-propylamine were purchased from Alfa Aesar (VWR, Mississauga, Ontario, Canada).

All solvents were used as received. Methanol was purchased from ACP Chemicals (Montreal, Quebec, Canada). Isopropanol was purchased from Calcdon Laboratories (Georgetown, Ontario, Canada). Tetrahydrofuran was purchased from EMD Chemicals (Gibbstown, N.J., US).

3-(dimethylamino)-1-Propylamine Functionalized PMMA (IVIW=15,000):

Polymethyl methacrylate (1.47 g, 14.7 mmol) was weighed into a 100 mL 2 neck round bottom flask with a stir bar and evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (15 mL) was added via syringe to the polymer and a reflux condenser was placed onto the flask. The mixture was heated to 150° C. for 3 days under nitrogen. After this time, the reaction mixture was a clear and colourless solution and was allowed to cool to room temperature causing a white precipitate to form. The liquid was decanted and the remaining solid was washed with 2-25 mL portions of isopropanol. It was then dried at 80° C. under high vacuum for 5 hours. The solid was then broken up with a spatula until more of a powder formed and then re-dried using the same conditions for 16 hours. 1.02 g of white powder was obtained and approximately 80% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.64 (bs, 3H, OCH₃), 2.86 (t, J=8.0 Hz, 2H, NHCH₂), 2.58 (t, J=8.0 Hz, 2H, Me₂NCH₂), 2.35 (s, 6H, N(CH₃)₂), 2.0-1.6 (b, 2H, backbone CH₂), 1.80 (m, 2H, CH₂CH₂CH₂), 1.2-0.7 (b, 3H, CH₃).

Large Scale Synthesis of 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=15,000):

Polymethyl methacrylate (40.0 g, 400 mmol) was weighed into a 1 L 2 neck round bottom flask with a stir bar and fitted with a condenser and rubber septum. The apparatus was evacuated on vacuum line/refilled with nitrogen three times. 3-(dimethylamino)-1-propylamine (350 mL) was poured into the flask under a flow of nitrogen. The mixture was heated to 150° C. for 4.5 days under nitrogen. After stirring overnight the reaction mixture was observed to be white and cloudy whereas after the full reaction time it was more a clear and colourless solution and was allowed to cool to room temperature. The condenser was removed under a flow of nitrogen and a distillation apparatus with condenser and receiving flask was attached. The reaction flask was covered in aluminum foil and the amine solvent distilled off under nitrogen atmosphere at 155° C. for 2 hours followed by 165° C. for 1 hour before being allowed to cool. The clear solid was then dried at 90° C. under high vacuum for 2 hours causing it to swell. The swollen solid was then broken up with a spatula and drying continued for 3 hours. It was then broken up with a spatula and drying continued for 2 hours. Grinding yielded a powder which was dried for 16 hours at 90° C. under high vacuum. 49.9 g of light yellow powder was obtained and approximately 80% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.65 (bs, 3H, OCH₃), 2.89 (t, J=8.0 Hz, 2H, NHCH₂), 2.61 (t, J=8.0 Hz, 2H, Me₂NCH₂), 2.38 (s, 6H, N(CH₃)₂), 2.0-1.6 (b, 2H, backbone CH₂), 1.82 (m, 2H, CH₂CH₂CH₂), 1.45-0.8 (b, 3H, CH₃).

23.3.1 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=35,000):

Polymethyl methacrylate (0.618 g, 6.17 mmol) was weighed into a 50 mL 2 neck round bottom flask with a stir bar and evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (4 mL) was added via syringe to the polymer and a reflux condenser was placed onto the flask. The mixture was heated to 150° C. for 16 hours under nitrogen. After this time, the reaction mixture was a light yellow liquid with yellow precipitate. The liquid was decanted and the remaining light yellow solid was dried at 80° C. under high vacuum for 2 hours. The solid was then broken up with a spatula until more of a powder formed and then re-dried using the same conditions for another 2 hours. This step was repeated once more after breaking up brittle chunks of the polymer using a mortar and pestle to give a fine powder (in order to facilitate drying). 0.695 g of yellow powder was obtained and approximately 50% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.64 (bs, 3H, OCH₃), 2.82 (t, J=8.0 Hz, 2H, NHCH₂), 2.53 (b, 2H, Me₂NCH₂), 2.31 (s, 6H, N(CH₃)₂), 2.0-1.6 (b, 2H, backbone CH₂), 1.76 (m, 2H, CH₂CH₂CH₂), 1.3-0.7 (b, 3H, CH₃).

Large Scale Synthesis of 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=35,000):

Polymethyl methacrylate (90.0 g, 899 mmol) was weighed into a 2 L 3 neck round bottom flask with a stir bar and fitted with a condenser, gas inlet and rubber septum. The apparatus was evacuated on vacuum line/refilled with nitrogen three times. 3-(dimethylamino)-1-propylamine (1 L) was poured into the flask under a flow of nitrogen. The mixture was heated to 150° C. for 5 days under nitrogen. After reacting overnight the mixture was observed to be a white suspension with stirring hampered by the solid. It was allowed to cool to room temperature. The condenser was removed under a flow of nitrogen and a distillation apparatus with condenser and receiving flask was attached. The reaction flask was covered in aluminum foil and the amine solvent distilled off under nitrogen atmosphere at 155° C. followed by 160° C. then 165° C. for 6 hours before being allowed to cool. A ¹H NMR spectrum was recorded of the distillate showing resonances corresponding primarily to 3-(dimethylamino)-1-propylamine along with methanol byproduct indicating successful reaction. ¹H NMR (400 MHz, CDCl₃) δ 3.28 (s, 3H, CH₃OH), 2.63 (t, J=8.0 Hz, 2H, NHCH₂), 2.20 (b, 2H, Me₂NCH₂), 2.11 (s, 6H, N(CH₃)₂), 1.50 (m, 2H, CH₂CH₂CH₂).

A small amount of residual liquid was decanted from the flask and the light yellow crystalline solid was washed quickly with 100 mL of isopropanol. It was then dried at 80° C. under high vacuum for 6 hours causing it to swell. The swollen solid was then broken up with a spatula and drying continued for 16 hours. Solid removed and ground yielding a light yellow powder which was added to a 1 L 2 neck round bottom flask and dried for 16 hours at 80° C. under high vacuum. 101.8 g of light yellow powder was obtained and approximately 80% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.64 (bs, 3H, OCH₃), 2.87 (t, J=8.0 Hz, 2H, NHCH₂), 2.59 (t, J=8.0 Hz, 2H, Me₂NCH₂), 2.36 (s, 6H, N(CH₃)₂), 2.0-1.6 (b, 2H, backbone CH₂), 1.82 (m, 2H, CH₂CH₂CH₂), 1.5-0.8 (b, 3H, CH₃).

23.3.2 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=120,000):

Polymethyl methacrylate (1.706 g, 17.0 mmol) was weighed into a 100 mL two-neck round bottom flask with a stir bar and evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (10 mL) was added via syringe to the polymer and a reflux condenser was placed onto flask. The mixture was heated to 150° C. for 16 hours under nitrogen. After this time, the reaction mixture was a light yellow liquid with yellow precipitate. The liquid was decanted and the remaining light yellow solid was dried at 80° C. under high vacuum for 2 hours. The solid was then broken up with a spatula until more of a powder formed and then re-dried using the same conditions for another 2 hours. This step was repeated once more after breaking up brittle chunks of polymer using a mortar and pestle to give a fine powder (in order to facilitate drying). 2.065 g of yellow powder was obtained and approximately 50% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.65 (bs, 3H, OCH₃), 2.81 (b, 2H, NHCH₂), 2.52 (m, 2H, Me₂NCH₂), 2.31 (s, 6H, N(CH₃)₂), 2.0-1.6 (b, 2H, backbone CH₂), 1.75 (m, 2H, CH₂CH₂CH₂), 1.3-0.7 (b, 3H, CH₃).

Large Scale Synthesis of 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=120,000):

Polymethyl methacrylate (47.14 g, 470.8 mmol) was weighed into a 1 L 2 neck round bottom flask with a stir bar and fitted with a condenser and gas inlet. The apparatus was evacuated on vacuum line/refilled with nitrogen three times. 3-(dimethylamino)-1-propylamine (350 mL) was poured into the flask under a flow of nitrogen. The mixture was heated to 150° C. for 3.5 days under nitrogen. After stirring overnight the reaction mixture was observed to remain clear and colourless with a white opaque gel precipitate. After full reaction time, the precipitate was a more compact, clear solid. It was allowed to cool to room temperature and the liquid decanted. The solid was then dried at 90° C. under high vacuum for 2 hours causing it to swell. The swollen solid was then broken up with a spatula and drying continued for 3 hours before being further broken up. Drying continued overnight. Very little of the hard crystalline mass was removed because it was difficult to do so. In order to soften solid it was heated to 170° C. under nitrogen before being put under vacuum causing the solid to inflate. It was then dried overnight at 100° C. under full vacuum. Flask cooled, solid removed and ground yielding 48.9 grams of white powder and approximately 80% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.64 (bs, 3H, OCH₃), 2.85 (t, J=8.0 Hz, 2H, NHCH₂), 2.56 (t, J=8.0 Hz, 2H, Me₂NCH₂), 2.34 (s, 6H, N(CH₃)₂), 1.95-1.55 (b, 2H, backbone CH₂), 1.82 (m, 2H, CH₂CH₂CH₂), 1.5-0.7 (b, 3H, CH₃).

3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=350,000):

Polymethyl methacrylate (1.47 g, 14.7 mmol) was weighed into a 100 mL two-neck round bottom flask with a stir bar and evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (15 mL) was added via syringe to the polymer and a reflux condenser was placed onto flask. The mixture was heated to 150° C. for 5.5 days under nitrogen. After stirring overnight, the reaction mixture was a clear, colourless liquid with clear, colourless precipitate. The liquid was decanted and the remaining white solid was washed with 2-25 mL portions of isopropanol before being dried at 100° C. under high vacuum for 2 hours. The solid was then broken up with a spatula until more of a powder formed and then re-dried using the same conditions for another 2 hours. The solid was then ground into more of a powder and dried for 2 hours, before being further ground and dried for 16 hours. 0.888 g of white powder was obtained and approximately 80% of the methacrylate sites were functionalized, as determined by integration of the appropriate resonances in the ¹H NMR spectrum.

¹H NMR (400 MHz, D₂O) δ 3.65 (bs, 3H, OCH₃), 2.84 (b, 2H, NHCH₂), 2.57 (b, 2H, Me₂NCH₂), 2.35 (bs, 6H, N(CH₃)₂), 1.95-1.55 (b, 2H, backbone CH₂), 1.79 (b, 2H, CH₂CH₂CH₂), 1.5-0.7 (b, 3H, CH₃).

Neutral Polyacrylic Acid (PAA) Based Materials

All reactions were conducted in air unless stated otherwise. NMR spectra were recorded on a Varian 400-MR NMR spectrometer (Agilent, Mississauga, Ontario, Canada). All NMR spectra are referenced against residual protonated solvent.

Polyacrylic acid samples (MW=1,800 and 450,000) were purchased from Sigma Aldrich Inc. (Oakville, Ontario, Canada). Polyacrylic acid (MW=50,000) was purchased from Polysciences Inc. (Warrington, Pa., USA) as a 25% solution in water. This was dried under vacuum on a rotary evaporator, washed with hexanes and dried further under vacuum giving the polymer as a white solid. 3-dimethylam ino-1-propylamine was purchased from Alfa Aesar (VWR, Mississauga, Ontario, Canada).

23.4.1 3-(Dimethylamino)-1-Propylamine Functionalized PAA (MW=1,800):

Polyacrylic acid (1.00 g, 13.88 mmol) was weighed into a 25 mL 2 neck round bottom flask with a stir bar and fitted with a gas inlet and rubber septum. The apparatus was evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (1.57 mL, 12.48 mmol) was added via syringe to the polymer and the reflux condenser was placed onto the flask. The mixture was heated to 160° C. for 2.5 days under nitrogen. After that time, the reaction mixture was a slightly cloudy colourless solution and was allowed to cool to 100° C. causing it to become more cloudy and stirring difficult. The mixture was dried at 100° C. for 6 hours under full vacuum followed by removal of the solid which was ground with a mortar and pestle giving a sticky white solid. The solid was further dried at 80° C. under full vacuum for 16 hours. The flask was cooled and 1.04 grams of white powder obtained.

¹H NMR (400 MHz, D₂O) δ 3.18 (m, 2H, NHCH₂), 2.41 (m, 2H, Me₂NCH₂), 2.24 (s, 6H, N(CH₃)₂), 2.20-1.95 (b, 1H, backbone CH), 1.71 (m, 2H, CH₂CH₂CH₂), 1.70-1.20 (b, 2H, backbone CH₂).

23.4.2 3-(Dimethylamino)-1-Propylamine Functionalized PAA (MW=50,000):

Polyacrylic acid (1.00 g, 13.88 mmol) was weighed into a 50 mL 2 neck round bottom flask with a stir bar and fitted with a gas inlet and rubber septum. The apparatus was evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (1.57 mL, 12.48 mmol) was added via syringe to the polymer and the reflux condenser was placed onto the flask. The mixture was heated to 160° C. for 24 hours under nitrogen. After that time, the reaction mixture was a clear yellow solution with stirring stopped. The mixture was dried at 100° C. under full vacuum for 3 hours causing the solid to swell. This solid was broken up with a spatula and re-dried using the same conditions for another 2 hours. The solid chunks were broken up in a mortar and pestle giving a powder which was further dried for 24 hours. The flask was cooled and 1.42 grams of light yellow powder obtained.

¹H NMR (400 MHz, D₂O) δ 3.18 (m, 2H, NHCH₂), 2.42 (m, 2H, Me₂NCH₂), 2.29 (s, 6H, N(CH₃)₂), 2.20-1.95 (b, 1H, backbone CH), 1.73 (m, 2H, CH₂CH₂CH₂), 1.80-1.25 (b, 2H, backbone CH₂).

23.4.3 3-(Dimethylamino)-1-Propylamine Functionalized PAA (MW=450,000):

Polyacrylic acid (1.00 g, 13.88 mmol) was weighed into a 50 mL 2 neck round bottom flask with a stir bar and fitted with a gas inlet and rubber septum. The apparatus was evacuated on vacuum line/refilled with nitrogen three times. A reflux condenser was also put under inert atmosphere using same procedure. 3-(dimethylamino)-1-propylamine (1.57 mL, 12.48 mmol) was added via syringe to the polymer and the reflux condenser was placed onto the flask. The mixture was heated to 160° C. for 2.5 days under nitrogen. After that time, stirring had stopped and the reaction mixture remained a wet light yellow solid. The mixture was dried at 100° C. under full vacuum for 4 hours giving a very hard solid. Parts of this solid were broken up with a spatula and re-dried using the same conditions for another 16 hours. The solid chunks were ground up and further dried for 24 hours. The flask was cooled and 0.363 grams of light yellow powder obtained.

¹H NMR (400 MHz, D₂O) δ 3.18 (m, 2H, NHCH₂), 2.41 (m, 2H, Me₂NCH₂), 2.27 (s, 6H, N(CH₃)₂), 2.20-1.90 (b, 1H, backbone CH), 1.72 (m, 2H, CH₂CH₂CH₂), 1.85-1.25 (b, 2H, backbone CH₂).

Ionic Polyacrylic Acid (PAA) Based Materials

All reactions were conducted in air unless stated otherwise. NMR spectra were recorded on a Varian 400-MR NMR spectrometer (Agilent, Mississauga, Ontario, Canada). All NMR spectra are referenced against residual protonated solvent. Centrifugation was conducted with a Sorvall Legend XT laboratory centrifuge (Thermo Fisher Scientific, Ottawa, Ontario, Canada).

Polyacrylic acid samples (MW=1,800 and 450,000) were purchased from Sigma Aldrich Inc. (Oakville, Ontario, Canada). Polyacrylic acid (MW=50,000) was purchased from Polysciences Inc. (Warrington, Pa., USA) as a 25% solution in water. This was dried under vacuum on a rotary evaporator, washed with hexanes and dried further under vacuum giving the polymer as a white solid. 3-dimethylamino-1-propylamine was purchased from Alfa Aesar (VWR, Mississauga, Ontario, Canada). (2-iodo-5-methoxyphenyl)boronic acid was prepared according to the literature reference: Al-Zoubi, R. M.; Marion, O.; Hall, D. G. Angew. Chem. Int. Ed. 2008, 47, 2876.

All solvents were used as received. Methanol was purchased from ACP Chemicals (Montreal, Quebec, Canada). Isopropanol was purchased from Calcdon Laboratories (Georgetown, Ontario, Canada). Tetrahydrofuran was purchased from EMD Chemicals (Gibbstown, N.J., US).

Ionic polymers were synthesized through a simple acid-base reaction between the acidic polymer and the basic amine yielding a salt of the polycarboxylate with an ammonium counterion.

(Polyacrylic Acid), 3-(Dimethylamino)-1-Propylammonium Salt (MW=1,800)

Polyacrylic acid (1.00 g, 13.88 mmol) was added to a 100 mL round-bottomed flask. Methanol (20 mL) was added and stirred giving a clear, colourless solution. 3-(dimethylamino)-1-propylamine (1.75 mL, 13.91 mmol) was added dropwise via syringe causing the immediate precipitation of a thick white solid which then disappeared after a few minutes. The solution was stirred overnight at 20° C. under air. The solvent was removed using a rotary evaporator giving a clear, colourless oil which was re-dissolved in 3 mL methanol. This concentrated solution was added dropwise to 500 mL of rapidly stirred tetrahydrofuran giving a white suspension which was stirred for 30 minutes before being allowed to settle. Most of the supernatant was decanted with the remaining 50 mL being transferred to a Nalgene bottle and centrifuged at 2000 rpm for 60 minutes. Remainder of supernatant decanted and solid dried under full vacuum at 20° C. for 4 hours. 1.05 grams of fine white powder isolated.

¹H NMR (400 MHz, D₂O) δ 3.08 (m, 4H, NHCH₂ and Me₂NCH₂), 2.77 (s, 6H, N(CH₃)₂), 2.30-1.95 (b, 1H, backbone CH), 2.08 (m, 2H, CH₂CH₂CH₂), 1.90-1.20 (b, 2H, backbone CH₂).

(Polyacrylic Acid), 3-(Dimethylamino)-1-Propylammonium Salt (MW=1,800):

Polyacrylic acid (1.51 g, 20.95 mmol) and (2-iodo-5-methoxyphenyl)boronic acid (0.291 g, 1.05 mmol) were added to a 500 mL Schlenk round-bottomed flask under nitrogen flush. Tetrahydrofuran (125 mL) was added and stirred for 30 minutes gradually giving a colorless, clear solution. 3-(dimethylamino)-1-propylamine (5.27 mL, 41.88 mmol) was then added via syringe resulting in the immediate formation of a thick white slurry. The resultant suspension was stirred for 2.5 days at 20° C. under nitrogen. The cloudy, white mixture was filtered through a Büchner funnel and the collected white solid was washed with 2-50 mL portions of tetrahydrofuran. The filter paper and solid were placed in a dessicator and dried under full vacuum at 20° C. for 6 hours. 2.20 grams of white solid were removed from the filter paper and crushed in a mortar and pestle giving a fine white powder which was judged to be suitably dry.

¹H NMR (400 MHz, D₂O) δ 3.01 (t, J=8.0 Hz, 2H, NHCH₂), 2.91 (t, J=8.0 Hz, 2H, Me₂NCH₂), 2.62 (s, 6H, N(CH₃)₂), 2.20-1.95 (b, 1H, backbone CH), 1.99 (m, 2H, CH₂CH₂CH₂), 1.80-1.20 (b, 2H, backbone CH₂).

(Polyacrylic Acid), 3-(Dimethylamino)-1-Propylammonium Salt (MW=50,000):

Polyacrylic acid (1.51 g, 20.95 mmol) and (2-iodo-5-methoxyphenyl)boronic acid (0.291 g, 1.05 mmol) were added to a 500 mL Schlenk round-bottomed flask under nitrogen flush. Methanol (200 mL) was added and stirred for 30 minutes gradually giving a colorless, clear solution. 3-(dimethylamino)-1-propylamine (5.27 mL, 41.88 mmol) was then added via syringe resulting in the immediate formation of a white suspension. The white solid redissolved over several minutes giving a clear and colorless solution. The reaction mixture was stirred overnight at 20° C. under nitrogen. The solution was decanted to a 500 mL round-bottomed flask and concentrated under vacuum giving a clear, semi-viscous liquid. The liquid was added dropwise to 900 mL of rapidly stirred isopropanol immediately giving a fine white solid. The stirring was stopped after 30 minutes but little solid settled so supernatant was transferred to Nalgene bottles and centrifuged at 2000 rpm for 1 hour causing complete separation of supernatant and white gel. The supernatant was decanted, the four Nalgene bottles placed inside a desiccator and dried overnight at 20° C. under high vacuum. The solid was then broken up using a mortar and pestle and dried at 80° C. for several hours giving 1.62 g of white powder.

¹H NMR (400 MHz, D₂O) δ 3.19 (t, J=8.0 Hz, 2H, NHCH₂), 3.07 (t, J=8.0 Hz, 2H, Me₂NCH₂), 2.85 (s, 6H, N(CH₃)₂), 2.2-1.9 (b, 1H, backbone CH), 2.12 (m, 2H, CH₂CH₂CH₂), 1.75-1.25 (b, 2H, backbone CH₂).

(Polyacrylic Acid), 3-(Dimethylamino)-1-Propylammonium Salt (MW=450,000):

Polyacrylic acid (1.51 g, 20.95 mmol) and (2-iodo-5-methoxyphenyl)boronic acid (0.291 g, 1.05 mmol) were added to a 500 mL Schlenk round-bottomed flask under nitrogen flush. Methanol (200 mL) was added and stirred for 30 minutes gradually giving a colorless, clear solution. 3-(dimethylamino)-1-propylamine (5.27 mL, 41.88 mmol) was then added via syringe resulting in the immediate formation of a white suspension. The white solid started to amalgamate after 1 minute into a lump which then proceeded to decrease in size over several minutes giving a clear and colorless solution. The reaction mixture was stirred overnight at 20° C. under nitrogen. The slightly cloudy solution was decanted to a 500 mL round-bottomed flask and concentrated under vacuum giving a clear, semi-viscous liquid. The liquid was added dropwise to 900 mL of rapidly stirred isopropanol immediately giving a white gel-like solid. Most of the supernatant was decanted while remaining suspension was transferred to Nalgene bottles and centrifuged at 2000 rpm for 1 hour causing complete separation of supernatant and white gel. The supernatant was decanted, the two Nalgene bottles placed inside a desiccator and dried overnight at 20° C. under high vacuum. The solid was then broken up using a mortar and pestle and dried at 80° C. for several hours giving 1.61 g of white powder.

¹H NMR (400 MHz, D₂O) δ 3.20 (m, 2H, NHCH₂), 3.09 (m, 2H, Me₂NCH₂), 2.87 (s, 6H, N(CH₃)₂), 2.2-1.95 (b, 1H, backbone CH), 2.13 (m, 2H, CH₂CH₂CH₂), 1.75-1.25 (b, 2H, backbone CH₂).

23.5 Polymethyl Methacrylate-Co-Styrene (PMMA/PS) Based Materials

All reactions were conducted in air unless stated otherwise. NMR spectra were recorded on a Varian 400-MR NMR spectrometer (Agilent, Mississauga, Ontario, Canada). All NMR spectra are referenced against residual protonated solvent.

Polystyrene-co-polymethyl methacrylate (1.4, 10, 20, and 31 mol % styrene) were purchased from Polymer Source (Montreal, Quebec, Canada). Polystyrene-co-polymethyl methacrylate (40 mol % styrene) was purchased from Sigma Aldrich Inc. (Oakville, Ontario, Canada). 3-dimethylamino-1-propylamine was purchased from Alfa Aesar (VWR, Mississauga, Ontario, Canada).

All solvents were used as received. Isopropanol was purchased from Calcdon Laboratories (Georgetown, Ontario, Canada).

23.5.1 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (40 mol % Styrene, MW=100,000-150,000):

Polystyrene-co-methyl methacrylate (2.938 g) was added to a 100 mL 2 neck round bottom flask and evacuated on vacuum line/refilled with nitrogen three times. Separately a reflux condenser was also put under an inert atmosphere using the same procedure. 3-(dimethylamino)-1-propylamine (20 mL) was added via syringe and the reflux condenser was placed onto the flask. The mixture was heated to 150° C. overnight under nitrogen. The resulting yellow solution was cooled to only 80° C. so that its viscosity didn't increase significantly; the solution was decanted slowly into 900 mL of rapidly stirred isopropanol giving a white-yellow precipitate that was filtered through a Buchner funnel. The polymer was dried at 80° C. under high vacuum for several hours giving a solid chunk, which was broken up with a mortar and pestle giving a light yellow solid. This was dried overnight at 80° C. under high vacuum. 2.85 grams of light yellow, water-insoluble powder was obtained.

¹H NMR (400 MHz, CDCl₃) δ 7.2-6.7 (b, 5H, aromatic CH), 3.52 (bs, 3H, OCH₃), 2.80 (b, 2H, NHCH₂), 2.39 (b, 2H, Me₂NCH₂), 2.23 (s, 6H, N(CH₃)₂), 2.1-1.4 (b, backbone CH₂ and CH), 1.68 (b, 2H, CH₂CH₂CH₂), 1.0-0.3 (b, backbone CH and CH₃).

23.5.2 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (31 mol % Styrene, MW=117,000-192,000):

Polystyrene-co-methyl methacrylate (1.13 g) was added to a 100 mL 2 neck round bottom flask and evacuated on vacuum line/refilled with nitrogen three times. Separately a reflux condenser was also put under an inert atmosphere using the same procedure. 3-(dimethylamino)-1-propylamine (15 mL) added via syringe and the reflux condenser was placed onto the flask. The mixture was heated to 150° C. overnight under nitrogen. The resulting clear, colorless solution was cooled to 20° C. causing a white gel to precipitate. The supernatant was decanted and the gel was washed with two 50 mL portions of isopropanol before being dried at 80° C. for 2 hours under high vacuum. The solid then broken up and drying was continued for another 2 hours under high vacuum. The solid was then broken up using a mortar and pestle and drying was continued overnight at 80° C. under high vacuum. 1.09 grams of white, water-insoluble powder was obtained.

¹H NMR (400 MHz, CDCl₃) δ 7.3-6.8 (b, 5H, aromatic CH), 3.55 (bs, 3H, OCH₃), 2.83 (b, 2H, NHCH₂), 2.42 (b, 2H, Me₂NCH₂), 2.26 (s, 6H, N(CH₃)₂), 2.0-1.5 (b, backbone CH₂ and CH), 1.71 (b, 2H, CH₂CH₂CH₂), 1.2-0.4 (b, backbone CH and CH₃).

23.5.3 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (20 mol % Styrene, MW=146,000-230,000):

Polystyrene-co-methyl methacrylate (1.075 g) was added to a 100 mL 2 neck round bottom flask and evacuated on vacuum line/refilled with nitrogen three times. Separately a reflux condenser was also put under an inert atmosphere using the same procedure. 3-(dimethylamino)-1-propylamine (15 mL) added via syringe and the reflux condenser was placed onto the flask. The mixture was heated to 150° C. overnight under nitrogen. The yellow solution was cooled to 80° C. causing a yellow gel to precipitate. The supernatant was decanted and the yellow thick gel was washed with two 50 mL portions of isopropanol before being dried at 80° C. for 2 hours under high vacuum. The solid was then broken up and drying continued for another 2 hours under high vacuum. The solid was then broken up using a mortar and pestle and drying was continued overnight at 80° C. under high vacuum. 1.15 grams of light yellow, water-soluble powder was obtained.

¹H NMR (400 MHz, D₂O) δ 7.5-6.8 (b, 5H, aromatic CH), 3.64 (bs, 3H, OCH₃), 2.76 (b, 2H, NHCH₂), 2.48 (b, 2H, Me₂NCH₂), 2.27 (s, 6H, N(CH₃)₂), 2.2-1.7 (b, backbone CH₂ and CH), 1.72 (b, 2H, CH₂CH₂CH₂), 1.4-0.5 (b, backbone CH and CH₃).

23.5.4 PMMA/PS (10 mol % Styrene, MW=10,600-15,900):

Polystyrene-co-methyl methacrylate (1.15 g, MW=10,600-15,900) was added to a 100 mL 2 neck round bottom flask and evacuated on vacuum line/refilled with nitrogen three times. Separately a reflux condenser was also put under an inert atmosphere using the same procedure. 3-(dimethylamino)-1-propylamine (15 mL) was added via syringe and the reflux condenser was placed onto the flask. The mixture was heated to 150° C. overnight under nitrogen. The resulting yellow solution was cooled to 80° C. causing a yellow gel to precipitate. The supernatant was decanted and the yellow thick gel was washed with two 50 mL portions of isopropanol before being dried at 80° C. for 2 hours under high vacuum. The solid was then broken up and drying was continued for another 2 hours under high vacuum. The solid was then broken up using a mortar and pestle and drying was continued overnight at 80° C. under high vacuum. 1.07 grams of light yellow, water-soluble powder was obtained.

¹H NMR (400 MHz, D₂O) δ 7.45-7.0 (b, 5H, aromatic CH), 3.65 (bs, 3H, OCH₃), 2.85 (t, J=8.0 Hz, 2H, NHCH₂), 2.56 (b, 2H, Me₂NCH₂), 2.34 (s, 6H, N(CH₃)₂), 2.1-1.6 (b, backbone CH₂ and CH), 1.79 (m, 2H, CH₂CH₂CH₂), 1.6-0.6 (b, backbone CH and CH₃).

23.5.5 PMMA/PS (1.4 mol % Styrene, MW=9,200-12,900):

Polystyrene-co-methyl methacrylate (1.09 g) was added to a 100 mL 2 neck round bottom flask and evacuated on vacuum line/refilled with nitrogen three times. Separately a reflux condenser was also put under an inert atmosphere using the same procedure. 3-(dimethylamino)-1-propylamine (15 mL) was added via syringe and the reflux condenser was placed onto the flask. The mixture heated to 150° C. overnight under nitrogen. The resulting yellow solution was cooled to room temperature causing a white gel to precipitate. The supernatant was decanted and the yellow thick gel was washed with three 50 mL portions of isopropanol before being dried at 80° C. for 2 hours under high vacuum. The solid was then broken up and drying was continued for another 2 hours under high vacuum. The solid was then broken up using a mortar and pestle and drying was continued overnight at 80° C. under high vacuum. 0.469 grams of white, water-soluble powder was obtained.

¹H NMR (400 MHz, D₂O) δ 7.4-7.0 (b, 5H, aromatic CH), 3.64 (bs, 3H, OCH₃), 2.86 (t, J=8.0 Hz, 2H, NHCH₂), 2.57 (b, 2H, Me₂NCH₂), 2.35 (s, 6H, N(CH₃)₂), 2.2-1.5 (b, backbone CH₂ and CH), 1.79 (m, 2H, CH₂CH₂CH₂), 1.5-0.5 (b, backbone CH and CH₃).

Polydiethylaminoethylmethacrylate (PDEAEMA) Based Materials

2-(diethylamino)ethyl methacrylate was purchased from Sigma-Aldrich, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] was purchased from Wako Pure Chemical Industries, Ltd. THF was purchased from Fisher Scientific. Size exclusion chromatography (SEC) was conducted using a Waters 2960 separation module with Styragel packed columns HR 0.5, HR 1, HR 3, HR 4, and HR 5E (Waters Division Millipore) coupled with a refractive index detector operating at 40° C.

Polydiethylaminoethylmethacrylate (PDEAEMA) MW=55,000

5.42 mL (5.0 g, 27.0 mmol) 2-(Diethylamino)ethyl methacrylate was placed in a 100 mL 2-neck round-bottom flask equipped with a 1 cm stir bar, a septum and condenser. 30 mL of THF and 0.050 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] were added. The reaction mixture was degassed at room temperature by bubbling argon through the solution using a single gauge needle under stirring with 600 rpm. After 1 h the needle was removed and the reaction mixture was heated to 65° C. for 5 h. After cooling to room temperature the solution was poured into a beaker equipped with a stir bar and 100 mL of cold water. The polymer precipitated over the 16 h under stirring to form a sticky gum-like solid that was collected with a spatula and dried in a dessicator for 24 h. The product was obtained as a sticky gum (2.7 g 54%)

¹H NMR (400 MHz, CDCl₃): δ=4.12-3.91 (m, 2H, OCH₂), 2.74-2.66 (m, 2H, CH₂CH₂N), 2.62-2.48 (m, 4H, CH₃CH₂N), 2.00-1.74 (m, 2H, CH₂ backbone), 1.14-0.96 (m, 6H, CH₃CH₂N), 0.95-0.82 (CCH₃);

¹³C NMR (100.7 MHz, CDCl₃): δ=177.4, 63.1 (OCH₂), 50.4 (CH₂CH₂N), 47.6 (CH₃CH₂N), 18.5 (CH₂ backbone), 16.6 (CCH₃), 12.0 (CH₃CH₂N);

GPC: (THF): M_(n): 31000, M_(w): 55,000, PDI: 1.78.

23.6.2 Polydiethylaminoethylmethacrylate (PDEAEMA) MW=69,000

5.42 mL (5.0 g, 27.0 mmol) 2-(diethylamino)ethyl methacrylate was placed in a 100 mL 2-neck round-bottom flask equipped with a 1 cm stir bar, a septum and condenser. 15 mL of THF and 0.050 g of 2,2′-azobis[2-(2-innidazolin-2-yl)propane] were added. The reaction mixture was degassed at room temperature by bubbling argon through the solution using a single gauge needle under stirring with 600 rpm. After 1 h the needle was removed and the reaction mixture was heated to 65° C. for 5 h. After cooling to room temperature the solution was poured into a beaker equipped with a stir bar and 100 mL of cold water. The polymer precipitated over the 16 h under stirring to form a sticky gum-like solid that was collected with a spatula and dried in a dessicator for 24 h. The product was obtained as a sticky gum (2.0 g, 40%)

¹H NMR (400 MHz, CDCl₃): δ=4.12-3.91 (m, 2H, OCH₂), 2.74-2.66 (m, 2H, CH₂CH₂N), 2.62-2.48 (m, 4H, CH₃CH₂N), 2.00-1.74 (m, 2H, CH₂ backbone), 1.14-0.96 (m, 6H, CH₃CH₂N), 0.95-0.82 (CCH₃);

¹H NMR (100.7 MHz, CDCl₃): δ=177.4, 63.1 (OCH₂), 50.4 (CH₂CH₂N), 47.6 (CH₃CH₂N), 18.5 (CH₂ backbone), 16.6 (CCH₃), 12.0 (CH₃CH₂N);

GPC: (THF): M_(n): 39000, M_(w): 69,000, PDI: 1.76.

Switchable Solubility of Polydiethylaminoethylmethacrylate (PDEAEMA) MW=69,000

800 mg of polydiethylaminoethylmethacrylate (PDEAEMA) MW=69000 was placed in a 100 mL round bottom flask equipped with a 1 cm stir bar. 60 mL of deionized water was added, CO₂ was introduced by means of a glass dispersion tube at 1 atm and the mixture was stirred at 900 rpm for 5 h at 50° C. Then the dispersion tube was removed, the flask closed with a glass stopper and the mixture was stirred for another 16 h at 50° C. The solution was then filtered off and the undissolved polymer weighed. 200 mg of the polymer did not dissolve. Therefore, the polymer has a solubility of 600 mg in 60 mL of carbonated water.

The solution was then bubbled with argon under heating at 60° C. After 10 min the solution turned turbid, and after 30 min, precipitate was visible. Bubbling with argon under heat was continued for another 30 min. Then the polymer was collected by filtration and the water evaporated. This left behind 5 mg of a solid that was analyzed by NMR. The NMR only showed traces of the polymer. The solubility of the polymer in water is therefore <1%.

Example 24: Viscosity Control with Switchable Water Additives

In order to study the use of switchable water additives in a method and system for viscosity control, a switchable additive or other molecule of interest was placed in a 50 mL round-bottom flask equipped with a 1 cm magnetic stir-bar and placed on a stir-plate. Water was added and the mixture was agitated at 600 rpm until the polymer was completely dissolved (1-24 h). The solution was then transferred in to a Technical Glass Products, Inc. C. F. Opage viscometer with either a 100 or 200 capillary tube. The measurements were taken at room temperature (i.e., from about 15-30° C.) and repeated twice. The solution was transferred back into the round bottom flask and CO₂ was introduced to the mixture by bubbling for 30 minutes at a flow rate of 80 ml/min. The carbonated solution was then put into the viscometer and the viscosity was measured three times. The viscosity in centistokes (cS) was calculated from the times the solution took to run through the viscometer.

24.1 Switchable Viscosity Using 3-(Dimethylamino)-1-Propylamine Functionalized Polymethylmethacrylate (MW=120,000)

Using the general method described above, 207.3 mg of PMMA (120,000) was dissolved in 20 mL H₂O and stirred for 1 h. Measurements were taken on the 200 viscometer. The viscosity change was reversed by removing the CO₂ through bubbling of Ar at 40° C. for 30 min. Measurements were taken again, leading to similar results obtained for the first run with no CO₂ present.

without CO₂ with CO₂ viscosity 8.3 cS 1.4 cS

24.2 Switchable Viscosity Using 3-(Dimethylamino)-1-Propylamine Functionalized Polymethylmethacrylate (MW=35,000)

Using the general method described above, 100.6 mg of PMMA (35,000) was dissolved in 10 mL H₂O and stirred for 1 h. Measurements were taken on the 200 viscometer.

without CO₂ with CO₂ viscosity 1.7 cS 1.2 cS

24.3 Switchable Viscosity Using Ionic Polyacrylic Acid (MW=450,000)

Using the general method described above, 54.9 mg of the ionic PAA (450,000) was dissolved in 10 mL H₂O and stirred for 1 h. Measurements were taken on the 200 viscometer.

without CO₂ with CO₂ viscosity 10.5 cS 4.0 cS

24.4 Switchable Viscosity Control Experiment Using Polyacrylamide (MW: 6,000,000)

Using the general method described above, 33.3 mg of polyacrylamide (MW: 6,000,000) was dissolved in 10 mL H₂O and stirred for 1 h. Measurements were taken on the 200 viscometer.

without CO₂ with CO₂ viscosity 6.9 cS 6.7 cS

These results demonstrate that the introduction of CO₂ did not change the viscosity of a solution of a non-switchable water polymer, even when the polymer was a very high molecular weight polymer.

24.5 Switchable Viscosity Control Experiment Using N,N-Dimethylcyclohexylamine

Using the general method described above, 104.6 mg of N,N-dimethylcyclohexylamine was dissolved in 10 mL H₂O and stirred for 1 h. Measurements were taken on the 100 viscometer.

without CO₂ with CO₂ viscosity 1.0 cS 1.0 cS

These results demonstrate that the introduction of CO₂ does not change the viscosity of a solution comprising a switchable water additive having a molecular weight that is too low to generate a substantial viscosity increase over water alone (which has a viscosity of about 1.0 cS at 20° C.), when the switchable water additive is in the non-ionized form.

24.6 Switchable Viscosity Using 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (PS 10 mol %, MW=10,600-15,900)

Using the general method described above, 150 mg of 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (PS 10 mol %) was dissolved in 7.5 mL H₂O and stirred for 1 h. Measurements were taken on the 100 viscometer.

without CO₂ with CO₂ viscosity 1.4 cS 1.1 cS

In this study, the switchable additive 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (PS 10 mol %) has a lower molecular weight than the additives tested above. As a result, the difference in viscosity between water alone and water plus the switchable additive 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (PS 10 mol %) is not as large as the difference observed using the polyamine switchable additives tested above. This study demonstrates a decrease in viscosity following the addition of CO₂, despite the fact that the presence of the non-ionic form of the switchable additive causes only a modest increase in viscosity over water alone. However, even with low molecular weight polymers, increasing the concentration of the polymer in a sample can also have a large effect on viscosity and, therefore, the relative change in viscosity when the additive is switched.

As demonstrated in this example, switchable water can be used effectively in a system having switchable viscosity. Selection of the appropriate switchable additive will, in part, depend on the degree of viscosity change required. If a large viscosity change is required, the switchable additive should have a relatively large molecular weight while remaining sufficiently soluble in water when in its non-ionic form to generate a substantial increase in viscosity in comparison to the viscosity of water alone. In systems where only a small viscosity change is desired, then the switchable water additive should be selected to have a relatively low molecular weight and be sufficiently soluble in water when in its non-ionic form to generate an increase in viscosity in comparison to the viscosity of water alone.

Example 25: Reversible Solvent Miscibility with Switchable Water Additives

25.1 Ceiling Salting Out Limits

NaCl, (NH₄)₂SO₄, d3-MeCN, MeOD were all purchased from Sigma Aldrich, Oakville. THF, ethyl acetate and acetonitrile were purchased from Fisher Scientific, Ottawa. Aliquots were taken using a Mettler-Toledo pipetor, all ¹H NMR acquired on a 400 MHz Bruker instrument.

Approximately 2 g of an organic solvent and approximately 2 g of water were mixed in a graduated cylinder. Small amounts of either NaCl or (NH₄)₂SO₄ were added to the solution to induce a salting out of the organic. Salt was continually added until the salted out organic maintained a constant volume above the aqueous layer. The volumes of each phase were recorded. Additional salt was often added past the observation of a consistent volume and no additional volume change occurred.

A 50 μL aliquot of the aqueous phase was extracted and placed in an NMR tube. The sample was diluted with a deuterated solvent. Approximately 20 mg of ethyl acetate was added to the NMR tube to act as an internal standard. A ¹H NMR spectrum was acquired and the peaks integrated. Knowing the amount of ethyl acetate and its corresponding integrations, the amount of organic solvent in the aqueous aliquot was calculated and multiplied to reflect the total amount of organic solvent still in the aqueous layer. Subtracting this value from the total mass of the organic solvent used in the experiment provided a ceiling percentage of organic solvent that could be salted out with inorganic salts. This experiment was carried out in triplicate using both salts for THF and acetonitrile. The results are presented in the table below.

Solvent Salt % Organic Salted Out THF NaCl 98 ± 0.5% THF (NH₄)₂SO₄ 99 ± 0.6% MeCN NaCl 93 ± 1.0% MeCN (NH₄)₂SO₄ 99 ± 0.1%

25.2 Acetonitrile-Water Forcing Out

Polyamines were investigated as additives for switchable ionic strength solutions useful in forcing out acetonitrile from an aqueous phase. To measure the extent of acetonitrile being forced out of an aqueous phase by an increase in ionic strength, and the amounts of polyamine that remained in the aqueous phase, 1:1 w/w solutions of acetonitrile and water were prepared in graduated cylinders. Three hundred milligrams of the additive were added and the cylinders were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in D₂O in NMR tubes. A known amount of dimethylformamide (DMF) was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired and through integration of the DMF standard, a concentration of acetonitrile or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase, giving a percentage of the compound being forced out or retained.

Acetonitrile Polymer retained Polymer forced out in aqueous phase EPEI (MW = 600) 60% 87% EPEI (MW = 1,800) 56% 71% EPEI (MW = 10,000) 55% 73% 3-(dimethylamino)-1-propylamine 66% 99% functionalized PMMA (MW = 35,000) 3-(dimethylamino)-1-propylamine 65-75%    99% functionalized PMMA (MW = 120,000) Polydiallylmethylamine 72% 99% Ionic PAA (MW = 1,800) 76% 99%

Following phase separation and collection of samples from each phase, argon was bubbled through the mixture while heating to 50° C. until the two phases recombined (typically from 15 to 60 min). The switching process (i.e., 30 min of CO₂ bubbling, sample collection, then 30 min of Ar bubbling) was successfully repeated, demonstrating that the reversible process can be cycled.

25.3 THF-Water Forcing Out

Polyamines were investigated as additives for switchable ionic strength solutions useful in forcing out THF from an aqueous phase. To measure the extent of THF being forced out of an aqueous phase by an increase in ionic strength, and the amounts of polyamine that remained in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. Three hundred milligrams of the additive were added and the cylinders were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the non-aqueous and aqueous layers were taken and dissolved in acetonitrile-d₃ in NMR tubes. A known amount of ethylacetate (EtOAc) was added to each NMR tube as an internal standard. ¹H NMR spectra were acquired and through integration of the EtOAc standard, a concentration of THF or additive was calculated and scaled up to reflect the total volume of the aqueous or non-aqueous phase, giving a percentage of the compound being forced out or retained.

Polymer retained Polymer THF forced out in aqueous phase EPEI (MW = 600) 76% 99% Functionalized PMMA 79% 99% (MW = 35,000)

Then argon was bubbled through the solution while heating to 50° C. until the two phases recombined (15 to 60 min). The switching process (i.e., 30 min of CO₂ bubbling, sample collection, then 30 min of Ar bubbling) was successfully repeated, demonstrating that the reversible process can be cycled.

25.4 Solvent Bridging with Switchable Water Additive

25.4.1 Ethyl Acetate & Water: CO₂-Induced Phase Separation:

0.531 g H₂O was mixed with 0.517 g ethyl acetate, generating a biphasic solution. The addition of 0.319 g N,N,A/W-tetramethyl-1,4-diaminobutane (TMDAB) bridged the two solvents into a single phase, clear, colourless solution (5:3:5 w/w/w H₂O:amine:organic). A stream of CO₂ was run over top of the solution for 5 minutes where an organic liquid phase began to cream out of the original monophasic solution.

25.4.2 n-Octanol & Water:

0.515 g H₂O was mixed with 0.315 g n-octanol, generating a biphasic solution. The addition of 0.498 g N,N,N′,N′-tetramethyl-1,4-diaminobutane (TMDAB) bridged the two solvents into a single phase, clear, colourless solution (5:5:3 w/w/w H₂O:amine:organic). A stream of CO₂ was run over top of the solution for 5 minutes where an organic liquid phase began to cream out of the original monophasic solution.

The above results demonstrate the successful use of switchable water in a system and method for reversing organic solvent miscibility. In such a system and method the switchable additive is selected such that it remains soluble in water when in its ionized form, but it is not necessary for the additive to be soluble in water when in the non-ionized form. In fact, in certain embodiments it may be beneficial for the additive to be insoluble or immiscible with water when it is in its non-ionized form. Additionally, in order to maximize the separation between the aqueous phase and the organic phase, the majority of additive should be retained in the aqueous layer when it is in its ionized form. That is, the ionized form of the additive should exhibit little or no solubility/miscibility with the organic solvent or little or no tendency to partition into the organic solvent from water.

Example 26: Solvent Drying with Switchable Water Additives

THF was from Fisher Scientific, Ottawa. CO₂ from Praxair, Belleville. Water content was determined on a Mettler-Toledo C20 coulometric Karl-Fischer titrator using a Hydranal Coulomat AK solution from Sigma Aldrich, Oakville. Samples were centrifuged on a Thermo Scientific IEC Medilite Centrifuge.

26.1 Dehydration of THF Using a Polymer

In a glass vial containing a stirbar, 102.8 mg of 3-(dimethylamino)-1-propylamine-functionalized poly(methyl methacrylate-co-styrene) (40 mol % styrene, MW=100,000-150,000) was dissolved a solution of 3.598 g THF (Fisher Scientific) and 0.398 g water (˜9:1 THF:H₂O w/w). The THF contained ˜1 wt % water as determined by Karl-Fischer titration so the initial water content of the solution was approximately 109,000 ppm. The vial was capped with a rubber septum and a single narrow gauge steel needle was inserted through the septum into the solution. A second needle was inserted into the septum, but not into the solution, to act as a gas outlet. CO₂ was introduced into the solution through the first needle at a flow rate of ˜10-20 mL min⁻¹ for 60 minutes while stirring. Some small white precipitate immediately formed and more formed during the course of CO₂ treatment. After 60 minutes, the needles were withdrawn and the vial was sealed and left to sit for several hours.

The solids did not settle out after a few hours so the mixture was centrifuged at 3100 RPM for 5 minutes causing the precipitate to settle. The liquid was decanted off and the water content analyzed by Karl-Fischer titration. The solution was found to have a water content of roughly 91,000 ppm, resulting in ˜17 of the water being removed via the polymer precipitate from CO₂ treatment.

26.2 Dehydration of Isobutanol Using a Polymer at Various Loadings

Isobutanol was from Sigma Aldrich, Oakville. CO₂ from Praxair, Belleville. Water content was determined on a Mettler-Toledo C20 coulometric Karl-Fischer titrator using a Hydranal Coulomat AK solution from Sigma Aldrich, Oakville.

Solutions of 4.5 g isobutanol and 0.5 g H₂O were made up in five separate glass vials containing stirbars. Varied amounts of 3-(dimethylamino)-1-propylamine-functionalized polymethyl methacrylate (MW=35,000) were dissolved into each solution. Vial 4 and 5 were blanks, with vial 4 containing the above polymer (with no later CO₂ treatment) and vial 5 containing unfunctionalized polymethyl methacrylate. The majority of the unfunctionalized polymethyl methacrylate did not dissolve in this solution. The initial water content of each vial was roughly 100,000 ppm.

Vial Loading of Polymer 1  50.4 mg 2 102.5 mg 3 150.8 mg  4* 103.8 mg  5**  99.5 mg *Functionalized polymer with no CO₂ treatment, **Unfunctionalized polymer with no CO₂ treatment.

Vials 1-3 were capped with rubber septa and a single narrow gauge steel needle was inserted through the septa into each solution. A second needle was inserted into the septa, but not into the solution, to act as a gas outlet. CO₂ was introduced into each solution through the first needle at a flow rate of ˜10-20 mL min⁻¹ for 30 minutes while stirring. Small white precipitate immediately formed and more formed during the course of CO₂ treatment. After 30 minutes, the needles were withdrawn and the vial was sealed and left to sit for 18 hours. Vials 4 and 5 were capped under air and left to sit for 18 hours.

After 18 hours, the liquid was removed from each vial and analyzed by Karl-Fischer titration. The remaining polymer that precipitated or did not dissolve initially was dried in a 120° C. oven overnight at 7 mm Hg pressure. The water content of the solutions after treatment and polymer recovered after treatment are described below.

Final Water % Water % Polymer Vial Content Removed Recovered 1 94,000 ppm 6% 56% 2 91,000 ppm 9% 44% 3 77,000 ppm 23%  45%  4* ~100,000 ppm 0%  0%  5** ~100,000 ppm 0% 65% *Functionalized polymer with no CO₂ treatment, **Unfunctionalized polymer with no CO₂ treatment.

26.3 Dehydration of a Mixed Organic Solvent with Polymers

Toluene and xylenes were purchased from Fisher Scientific, Ottawa. Silica and methyl ethyl ketone were from Sigma Aldrich, Oakville. Ethanol was from Commerical Alcohols, Brampton and CO₂ was from Praxair, Belleville. Water content was determined on a Mettler-Toledo C20 coulometric Karl-Fischer titrator using a Hydranal Coulomat AK solution from Sigma Aldrich, Oakville.

In a glass vial containing a stirbar, 49.2 mg of 3-(dimethylamino)-1-propylannine-functionalized poly (methyl methacrylate-co-styrene) (40 mol % styrene, MW=100,000-150,000) was dissolved in 1.900 g 3:3:3:1 v/v methyl ethyl ketone:toluene:xylenes:ethanol. The addition of 0.102 g water (to give a −19:1 organic:H₂O w/w solution) caused some polymer to precipitate out of solution. The initial water content of the mixture was 51,000 ppm; however the actual amount of water dissolved into the organic solvent resulted in organic solution with a water content of −17,000 ppm. The vial was capped under air, stirred for 60 minutes and then left to sit for 24 hours.

In a 2^(nd) glass vial container a stirbar, 50.1 mg of 3-(dimethylamino)-1-propylamine-functionalized poly(methyl methacrylate-co-styrene) (40 mol % styrene, MW=100,000-150,000) was dissolved in 1.903 g 3:3:3:1 v/v methyl ethyl ketone:toluene:xylenes:ethanol. The addition of 0.107 g water (to give a ˜19:1 organic:H₂O w/w solution) caused some polymer to precipitate out of solution. The initial water content of the mixture was approximately 53,000 ppm; however the actual amount of water dissolved into the organic solvent resulted in organic solution with a water content of ˜17,000 ppm. This vial was capped with a rubber septum. A single narrow gauge steel needle was inserted through the septum into the solution. A second needle was inserted into the septum, but not into the solution, to act as a gas outlet. CO₂ was introduced into the solution through the first needle at a flow rate of ˜10-20 mL min⁻¹ for 60 minutes while stirring. After 60 minutes, the needles were withdrawn and the vial was sealed and left to sit for 24 hours.

After 24 hours, the liquid was decanted off from the polymer and the water content was analyzed by Karl-Fischer titration. The first solution, the blank, was found to have a water content of roughly 16,600 ppm, resulting in ˜2% of the water being removed via the polymer. The solution from the 2^(nd) vial had a water content of 13,800 ppm, resulting in a ˜19% removal of water by the polymer with CO₂ treatment.

The polymer was dried for 18 hours in a 140° C. oven and weighed to determine the amount of polymer that did not precipitate during treatment and is thus lost. The blank was found to have lost 22% of the original polymer mass and the CO₂-treated solution lost 46% of the original polymer.

26.4 Dehydration of Isobutanol with a Polymer and Recycling of the Polymer

Isobutanol was purchased from Sigma Aldrich, Oakville and CO₂ was from Praxair, Belleville. Water content was determined on a Mettler-Toledo C20 coulometric Karl-Fischer titrator using a Hydranal Coulomat AK solution from Sigma Aldrich, Oakville.

In a glass vial container a stirbar, 28.0 mg of 3-(dimethylamino)-1-propylamine-functionalized poly(methyl methacrylate-co-styrene) (40 mol % styrene, MW=100,000-150,000) was dissolved in 4.546 g isobutanol and 0.509 g H₂O. The initial water content of the solution was 100,700 ppm. This vial was capped with a rubber septum. A single narrow gauge steel needle was inserted through the septum into the solution. A second needle was inserted into the septum, but not into the solution, to act as a gas outlet. CO₂ was introduced into the solution through the first needle at a flow rate of ˜10-20 mL min⁻¹ for 60 minutes while stirring at which point solids began to precipitate. After 60 minutes, the needles were withdrawn and the liquid was decanted off. The water content was analyzed by Karl-Fischer titration and found to be 92,000 ppm, a roughly 9% reduction in water content.

The precipitated polymer was dried for 18 hours in a 80° C. oven. The solid was then weighed and it was found that approximately 50% was lost during the 1^(st) cycle. The remaining polymer was redissolved in 2.274 g of isobutanol and 0.265 g H₂O. The water content was 104,400 ppm. The mixture underwent a CO₂-treatment similar to the procedure outlined above. Once again the polymer precipitated during CO₂ treatment. The liquid was decanted off and the water content was found to be 95,000 ppm, representing an approximately 9% decrease in water content on the 2^(nd) cycle.

26.5 Dehydration of a Mixed Organic Solvent with a Polymer with Recycling of the Polymer

Toluene and xylenes were purchased from Fisher Scientific, Ottawa. Silica and methyl ethyl ketone were purchased from Sigma Aldrich, Oakville. Ethanol was from Commerical Alcohols, Brampton and CO₂ from Praxair, Belleville. Water content was determined on a Mettler-Toledo C20 coulometric Karl-Fischer titrator using a Hydranal Coulomat AK solution from Sigma Aldrich, Oakville.

In a glass vial containing a stirbar, 25.8 mg of 3-(dimethylamino)-1-propylamine-functionalized poly(methyl methacrylate-co-styrene) (40 mol % styrene, MW=100,000-150,000) was dissolved in 1.951 g 3:3:3:1 v/v methyl ethyl ketone:toluene:xylenes:ethanol. The addition of 0.107 g water (to give a ˜19:1 organic:H₂O w/w solution) caused some polymer to precipitate out of solution. The initial water content of the mixture was 50,100 ppm; however the actual amount of water dissolved into the organic solvent resulted in organic solution with a water content of ˜17,000 ppm. This vial was capped with a rubber septum. A single narrow gauge steel needle was inserted through the septum into the solution. A second needle was inserted into the septum, but not into the solution, to act as a gas outlet. CO₂ was introduced into the solution through the first needle at a flow rate of ˜10-20 mL min⁻¹ for 60 minutes while stirring where solids continued to precipitate. After 60 minutes, the needles were withdrawn and the liquid was decanted off. The water content was analyzed by Karl-Fischer titration and found to be 15,900 ppm, a roughly 6% reduction in water content.

The precipitated polymer was dried for 18 hours at 80° C. The solid was then weighed and it was found approximately 26% was lost during the 1^(st) cycle. The remaining polymer was redissolved in 1.900 g of 3:3:3:1 v/v methyl ethyl ketone:toluene:xylenes:ethanol. The addition of 0.096 g water (to give a ˜19:1 Org:H₂O w/w solution) caused some polymer to precipitate out of solution. The water content of the mixture was 48,100 ppm; however, the actual amount of water dissolved into the organic solvent resulted in organic solution with a water content of ˜17,000 ppm. The mixture underwent a CO₂-treatment similar to the procedure outlined above. Once again, more polymer precipitated during CO₂ treatment. The liquid was decanted off and the water content was found to be 11,900 ppm, representing a ˜30% decrease in water content on the 2^(nd) cycle.

Example 27: Clay Settling with Switchable Water Additives

Montmorillonite (bentonite) from Panther Creek, Colo., USA was purchased from Ward's Natural Science. Kaolinite (China Clay) from Panther Creek, Colo., USA was purchased from Ward's Natural Science.

In this study an equal amount of polyamine was placed into two different 250 mL round bottom flasks equipped with a 2 cm Teflon stir-bar. 100 mL deionized water was added and the solutions were stirred (600 rpm) until the polymer dissolved (10 min to 16 h). Then 1 g of Montmorillonite was added. Both suspensions were stirred at 600 rpm for 1 h, while CO₂ was bubbled through one of the solutions using a gas dispersion tube. After that, both suspensions were transferred into 100 mL graduated cylinders and the settling rate was monitored over time. After 16 hours samples of both supernatants were taken and the turbidity was measured on a Orbeco-Hellige TB200 turbidity meter. The range of the instrument is 0-1100 NTU.

27.1 Butylated Polyethyleneimine (BPEI), MW=600

27.1.1 Butylated Polyethyleneimine (BPEI), MW=600 Low Concentration

Thirty-six milligrams of BPEI, MW=600 were used in the method set out above. As shown in FIGS. 23A and 23B, the clay settles both with and without CO₂ present, with a faster settling rate without CO₂ present. Importantly, however, in the presence of CO₂ the supernatant was less turbid.

27.1.2 Butylated Polyethyleneimine (BPEI), MW=600 High Concentration

Seventy-eight milligrams of BPEI, MW=600 were used in the method set out above. The presence of CO₂ caused the clay to flocculate on top as a voluminous layer (40%) leaving a clear phase behind (see FIG. 24). Without CO₂ the clay settled slowly with a turbid supernatant after 16 hour settling time.

lower clear layer supernatant without CO₂ with CO₂ Turbidity (after 16 h) 390 NTU 11 NTU

Propylated Polyethyleneimine (PPEI) MW=600

Fifty-six milligrams of PPEI, MW=600 were used in the method set out above. The clay settles both with and without CO₂ present, with a faster settling rate with CO₂ present. However, the clay becomes very voluminous and settles only to 59% of the starting value after 24 h. Supernatant is clearer in the presence of CO₂.

lower clear layer supernatant without CO₂ with CO₂ Turbidity (after 2 h) 263 NTU 4 NTU

27.2 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=120,000)

Forty six milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) was used in the method set out above. The settling was slightly faster without CO₂ present (see, FIG. 25). During the settling process, the supernatant was less turbid in the presence of CO₂. The turbidity measurement was taken after 2 hours.

supernatant without CO₂ supernatant with CO₂ Turbidity (after 2 h) 371 NTU 6 NTU

27.3 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (10 Mol % Styrene, MW=10,600-15,900)

Forty three milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (10 mol % styrene, MW=10,600-15,900) was used in the method set out above. Without CO₂ bulk settling is impossible to observe due to high turbidity of supernatant. With CO₂ settling is slow but produces very clear supernatant. See FIGS. 26A and 26B.

supernatant without CO₂ supernatant with CO₂ Turbidity (after 16 h) 1100 NTU 10 NTU

27.5 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=120,000)

Forty nine milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) was used in the method set out above with the modification that 1 g kaolinite was used instead of montmorillonite. Instantaneous bulk settling was observed in the presence of CO₂ leaving a slightly turbid supernatant behind, which cleared out over 2 hours. See FIG. 27. Without CO₂ fast bulk settling was observed, however, the supernatant was very turbid.

supernatant without CO₂ supernatant with CO₂ Turbidity (after 2 h) 1100 NTU 25 NTU

3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=350,000)

Forty nine milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=350,000) was used in the method set out above with the modification of 2 g kaolinite being used instead of montmorillonite. Very fast bulk settling was observed both in the presence and absence of CO₂. Supernatant less turbid with CO₂.

supernatant without CO₂ supernatant with CO₂ Turbidity (after 2 h) 1100 NTU 28 NTU

Neutral 3-(Dimethylamino)-1-Propylamine Functionalized PAA (MW=50,000)

Fifty milligrams of neutral 3-(dimethylamino)-1-propylamine functionalized PAA (MW=50,000) was used in the method set out above. Without CO₂ bulk settling is slower and supernatant more turbid than with CO₂.

supernatant without CO₂ supernatant with CO₂ Turbidity (after 2 h) 62 NTU 1 NTU

Study Using Hydrochloric Acid and 3-(Dimethylamino)-1-Propylamine Functionalized PMMA MW=120,000

Fifty milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) was used in the method set out above. To one of the suspensions, 45 μL of 4 M hydrochloric acid was added as opposed to acidifying the water by bubbling with carbon dioxide used previously. Both suspensions were stirred for 30 min, then transferred to graduated cylinders and the settling monitored over time. In the presence of hydrochloric acid, the settling was slightly faster and the supernatant slightly clearer than without the acid.

supernatant without acid supernatant with acid Turbidity (after 2 h) 23 NTU 5 NTU

Study Using Sulfuric Acid and 3-(Dimethylamino)-1-Propylamine Functionalized PMMA MW=120,000

Fifty milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) was used in the method set out above. To one of the suspensions, 180 μL of 1 M sulfuric acid was added as opposed to acidifying the water by bubbling with carbon dioxide used previously. Both suspensions were stirred for 30 min, then transferred to graduated cylinders and the settling monitored over time. In the presence of sulfuric acid, the settling was very fast (47% of the starting height after 2 h) and the supernatant slightly clearer than without the acid. Settling in the absence of sulfuric acid was slow (79% of the starting height after 2 h).

supernatant without acid supernatant with acid Turbidity (after 2 h) 25 NTU 1 NTU

Study Using Formic Acid and 3-(Dimethylamino)-1-Propylamine Functionalized PMMA MW=120,000

Fifty milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) was used in the method set out above. To one of the suspensions, 1.8 mL of 0.1 M formic acid was added as opposed to acidifying the water by bubbling with carbon dioxide used previously. Both suspensions were stirred for 30 min, then transferred to graduated cylinders and the settling monitored over time. In the presence of formic acid, the settling was very fast (33% of the starting height after 2 h) but the supernatant more turbid than without the acid. Settling in the absence of formic was slow (74% of the starting height after 2 h).

supernatant without acid supernatant with acid Turbidity (after 2 h) 24 NTU 116 NTU

27.6 Control Experiment Using Polyacrylamide, MW=6,000,000

Thirty-one milligrams of polyacrylamide, MW=6,000,000 was used in the method set out above. Very fast settling rates were observed both in the present and absence of CO₂ leaving very clear supernatants behind (see FIGS. 28A and 28B). In the presence of CO₂ some clay particles were observed floating on top and in the supernatant.

supernatant without CO₂ supernatant with CO₂ Turbidity (after 16 h) 20 NTU 27 NTU

Example 28: Osmotic Pressure Effects of Switchable Water Additives

Formation of ionic species in the presence of switchable water additives and suitable trigger(s) leads to an increase in osmotic pressure due to an increase in higher unit solute concentrations.

The switchable osmotic pressure measurements were conducted on a Zimm-Meyerson osmometer using Sterlitech UTC-80LB toray flat sheet membranes. A 0.1% (w/v) switchable polyamine solution in water was made by dissolving 20 mg of the corresponding polyamine in 20 mL deionized H₂O. After the polyamine was completely dissolved, 13 mL of the solution was transferred into the glass cell of the osmometer and the outer glass cell was filled with deionized water. The system was closed with a lid and allowed to reach equilibrium overnight. Measurements of the capillary tube and the control capillary were taken. The draw solution was then taken out of the cell and transferred into a graduated cylinder. Both the draw solution and the solution of the outer cell were carbonated by bubbling CO₂ with a gas dispersion tube for 1 h. The draw solution was transferred back into the glass cell of the osmometer, the system was closed and held under an atmosphere of CO₂. A constant flow of CO₂ was maintained using two gauche needles, one of them connected to a CO₂ source with a flow rate of 10 ml/min. The heights taken were height differences of the capillary tube connected to the cell and the control capillary tube. Based on these heights the hydrostatic pressure was calculated using the equation: Π=ρhg where Π is the hydrostatic pressure, ρ is the density of the solution, h is the height of the water column and g is the force of gravity. Hydrostatic pressure is taken to be proportional to osmotic pressure of the solution at equilibrium.

28.1 Switchable Osmotic Pressure Experiment Using BPEI, MW=600

Twenty-eight milligrams of BPEI was suspended in 20 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase BPEI, MW = 600 363 Pa 2433 Pa 6.7

28.2 Switchable Osmotic Pressure Experiment Using BPEI, MW=10,000

Twenty-seven milligrams of BPEI was suspended in 25 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase BPEI, MW = 10,000 88 Pa 618 Pa 7.0

28.3 Switchable Osmotic Pressure Experiment Using Ionic PAA (MW=450,000):

Twenty-milligrams of ionic PAA (MW=450,000) with 3-(dimethylamino)-1-propylammonium counterion were dissolved in 20 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase Ionic PAA 29 Pa 450 Pa 15.5 (MW = 450,000)

28.4 Switchable Osmotic Pressure Experiment Using 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=120,000):

Forty-six milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) were dissolved in 46 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase functionalized 137 Pa 1923 Pa 14.0 PMMA (MW = 120,000)

28.5 Switchable Osmotic Pressure Experiment Using 3-(Dimethylamino)-1-Propylamine Functionalized PMMA (MW=35,000):

Sixteen milligrams of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=35,000) were dissolved in 48 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase functionalized 412 Pa 1687 Pa 4.1 PMMA (MW = 35,000)

After treatment with CO₂ and measurement of osmotic pressure, the solution was taken out of the osmometer and heated to 50° C. with nitrogen sparging for 6 hours. The hydrostatic pressure of the solution was then measured and found to be 638 Pa.

28.6 Switchable Osmotic Pressure Experiment Using 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (1.4 Mol % Styrene, MW: 9,200-12,900)

12 mg of 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (1.4 mol % styrene, MW: 9,200-12,900) were dissolved in 38 mLl of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase functionalized 226 Pa 1403 Pa 6.0 PMMA/PS (1.4 mol % styrene)

28.7 Switchable Osmotic Pressure Experiment Using 3-(Dimethylamino)-1-Propylamine Functionalized PMMA/PS (10 mol % Styrene, MW: 10,600-15,900)

13 mg of 3-(dimethylamino)-1-propylamine functionalized PMMA/PS (10 mol % styrene, MW: 10,600-15,900) were dissolved in 40 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase functionalized 118 Pa 1785 Pa 15.0 PMMA/PS (10 mol % styrene)

Switchable Osmotic Pressure Experiment Using Neutral 3-(Dimethylamino)-1-Propylamine Functionalized PAA (MW=1,800)

Nine milligrams of 3-(dimethylamino)-1-propylamine functionalized PAA (MW=1,800) were dissolved in 36 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase functionalized PAA 287 Pa 1579 Pa 5.5 (MW = 1,800)

Switchable Osmotic Pressure Experiment Using PDEAEMA (MW=55,000)

Fifty-four milligrams of PDEAEMA were dissolved in 54 mL of carbonated water. Height measurements were only taken of the carbonated solution, as the polymer was not soluble in non-carbonated water.

hydrostatic pres- hydrostatic pressure sure without CO₂ pressure with CO₂ increase PDEAEMA (MW = Not soluble 1957 Pa 55,000)

28.8 Switchable Osmotic Pressure Control Experiment Using N,N-dimethylcyclohexylamine:

Forty-eight milligrams of N,N-dimethylcyclohexylamine were dissolved in 21 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure with CO₂ pressure with CO₂ increase N,N-dimeth- 580 Pa 1550 Pa 2.7 ylcyclohexylamine

28.9 Switchable Osmotic Pressure Control Experiment Using Polyacrylamide (MW=6,000,000):

Twenty milligrams of polyacrylamide were dissolved in 20 mL of deionized water. Height measurements were taken before and after CO₂ treatment.

hydrostatic pres- hydrostatic pressure sure with CO₂ pressure with CO₂ increase polyacrylamide 98.1 Pa 176 Pa 1.8 (MW = 6,000,000)

As demonstrated using polyacrylamide, only a very small change in pressure can be achieved by the addition of CO₂ in the absence of a switchable additive. Further, the switchable tertiary amine tested in 28.8 was capable of generating a lower change in osmotic pressure than the polyamines, but more than observed for polyacrylamide.

Example 29: Homogenous Catalysis Using Switchable Water Additives

Homogeneous catalysts are often more active and selective than heterogeneous catalysts but are far more difficult to separate from the product. The development of means to separate, recover, and recycle homogeneous catalysts is an important area of research for both industry and academia (Catalyst Separation, Recovery and Recycling: Chemistry and Process Design, D. J. Cole-Hamilton, R. Tooze, Eds., Springer, Dordrecht, 2006; M. J. Muldoon, Dalton Trans., 2010, 39, 337). One approach, already industrialized in a few cases, is catalysis in a biphasic mixture of two solvents (B. Cornils, E. G. Kuntz, Aqueous-Phase Organometallic Catalysis 2nd ed., B. Cornils, W. G. Hermann, Eds., Wiley-VCH, Weinheim, 2004; U. Hintermair, W. Leitner, P. G. Jessop, Supercritical Solvents, W. Leitner, P. G. Jessop, Eds., Wiley/VCH Weinheim, 2010). Such reactions involve the dissolution of a catalyst into one of the solvents and the dissolution of the reagents into the other solvent. The small partitioning of the reagent into the solvent containing the catalyst allows the reaction to proceed. Aqueous/organic biphasic systems are of great interest and are currently in use for the industrial hydroformylation of low carbon number-containing alkenes (B. Cornils, E. G. Kuntz, Aqueous-Phase Organometallic Catalysis 2nd ed., B. Cornils, W. G. Hermann, Eds., Wiley-VCH, Weinheim, 2004). These systems often utilize transition metals ligated by sulfonated phosphines to increase the water solubility of the metal, causing the catalyst to reside in the aqueous phase. After the reaction is completed, the product (organic) phase is decanted and the aqueous catalyst-containing phase is used again.

Aqueous/organic biphasic catalysis of this type has both advantages and disadvantages. An advantage of this method is, of course, the easy separation of catalyst from product. A key disadvantage is the slow rate of reaction that results from the catalyst and the reactants being in two different phases, especially when the reactant (such as 1-octene or styrene) has very poor solubility in water. One solution to this problem is to design a trigger to make the aqueous and organic phases merge into one phase during the catalysis and then to separate into two phases again after the reaction is complete. This can be accomplished using high pressure CO₂ as a trigger (THF and water are miscible when high pressure CO₂ is absent and form two liquid phases when high pressure CO₂ is present) (J. Lu, M. L. Lazzaroni, J. P. Hallet, A. S. Bommarius, C. L. Liotta, C. A. Eckert, Ind. Eng. Chem. Res., 2004, 43, 1586). The present example provides a method for achieving the same result using only 1 atm of CO₂.

A switch of miscibility for organic solvents in water can provide an organic/aqueous mixture of solvents that is monophasic during homogeneous catalysis and then switched to biphasic by the introduction of CO₂ after the catalysis is complete. The process involves homogeneous catalysis (such as hydroformylation of an alkene) in a water/organic solvent monophasic mixture that also contains a small amount of a soluble amine (FIG. 29). After the catalysis is complete, CO₂ is added reacting with the amine, causing a rise in the ionic strength of the solution and thereby triggering the salting out of both the organic solvent and the product from the aqueous phase. If a suitably hydrophilic catalyst is selected, the catalyst remains in the aqueous phase isolated from the products or reaction. After decantation of the product phase, the removal of CO₂ from the water regenerates a low ionic strength aqueous phase that can accept fresh reagents and THF and the reaction can be repeated.

The hydroformylation of styrene is an attractive model system because its aldehyde products have potential use in pharmaceutical and fine chemical production and its water solubility is low (CRC Handbook of Chemistry and Physics, 79^(th) ed. D. R. Lide, Ed., CRC Press, Boca Raton, 1998), which make a traditional aqueous/organic biphasic reaction inefficient. Our other examples of switchable water showed that THF could easily be forced out of aqueous solution with the application of CO₂. Our initial studies into hydroformylation of styrene found that this weakly coordinating organic solvent may hinder the hydroformylation reaction. We therefore searched for other water-miscible organic solvents that could solubilize styrene and could also be salted out by a switchable water additive in the presence of CO₂, and found that tert-butanol is one appropriate organic solvent choice.

Styrene Hydroformylation in the Presence of Switchable Water Additive:

To a 10 mL 3:2 t-BuOH:H₂O (v/v) mixture, 0.5 g N,N-dimethylethanolamine (DMEA) was added as the amine additive to create a 1.4 molal solution (relative to water). Styrene (0.15 mL), [Rh(COD)Cl]₂, and TPPTS were added (Rh=0.5 mol % relative to styrene, P/Rh=7, COD=cyclooctadiene, TPPTS=tris(3-sulfophenyl)phosphine trisodium salt hydrate). This generated a single phase pale yellow solution (FIG. 30, top left). The solution was transferred to a pressure vessel, heated to 100° C., pressurized to 5 bar with synthesis gas (1:1 CO:H₂), and allowed to react for 3 h. After the reaction, CO₂ was bubbled through the solution, generating a biphasic system with the catalyst residing in a dark red-brown aqueous phase and the product residing in the clear, colorless t-BuOH phase. The organic phase was removed and analyzed. The aqueous phase was heated to 65° C. and N₂ was bubbled through it in order to remove the CO₂ and lower the ionic strength of the solution. This process changed the aqueous phase to a golden yellow colour. A fresh supply of t-BuOH, styrene, water (to account for some evaporation) and TPPTS (3 Rh equivalents for each cycle, which brought the final P/Rh ratio to 13) was added. The catalysis and separation process was performed for three cycles, giving consistently high conversion, good aldehyde selectivity and good regioselectivity towards the branched isomer (see Entry 1 in the table below). By-products were identified as the hydrogenated product, ethylbenzene, and acetophenone; the last of these forms through a completely different mechanism to the hydroformylation when advantageous molecular oxygen is present (rhodium can catalyze the oxidation reaction of terminal alkenes with molecular oxygen to give methyl ketones, see: (a) H. Mimoun, M. P. Machirant, I. S. de Roch, J. Am. Chem. Soc., 1977, 100, 5437. (b) O. Bortolini, F. di Furia, G. Modena, R. Seraglia, J. Mol. Cat., 1984, 22, 313. (c) G. A. Olah, Á. Molnár, Hydrocarbon Chemistry 2^(nd) ed.; John Wiley and Sons, Hoboken, 2003).

It was found that the addition of more TPPTS through each cycle was necessary to maintain good conversions and selectivities. Without additional TPPTS added before each addition of fresh reactant, the aqueous phase progressively darkened through the cycles and black precipitate formed. Conversions then decreased sharply through the cycles (see Entry 2 in the table below). Without wishing to be bound by theory, the likely cause of these observations is oxidation of TPPTS, deactivating the catalyst. Even under stringent oxygen-free conditions (see Entry 3 in the table below), the addition of additional TPPTS was necessary as conversions eventually decreased upon recycling, although the aldehyde selectivity was improved compared to Entry 1 below where the recycling processes were carried out in air.

Cycle 1 Cycle 2 Cycle 3 % Conversion/% % Conversion/% % Conversion/% Additive Aldehyde Selectivity B/L Aldehyde Selectivity B/L Aldehyde Selectivity B/L DMEA ^(b) 98.9/96.1 8.0 99.4/89.3 6.8 97.2/97.0 6.5 DMEA ^(c) 98.5/91.1 8.8 87.9/87.7 6.3 40.7/88.5 5.3 DMEA ^(d) 95.3/98.9 8.8 96.3/99.0 6.5 73.7/98.1 5.7 TMDAB ^(c, e) 85.2/87.7 7.7 43.8/87.3 5.4  8.9/85.2 4.6 ^(a) Conditions: Reaction mixture was comprising 6 mL tert-butanol, 4 mL H₂O, 1.4 molal of an amine additive, 0.25 mol % catalyst, and 7:1 P:Rh. Reaction was run at 100° C. at 5 bar syn gas (1:1 CO:H₂) for 3 hours. Yields were determined by GC with the assistance of previously-prepared calibration curves. ^(b) Average of two runs, 3 equivalents of TPPTS in regard to Rh added during each cycle for a final ratio of 13:1 P:Rh. ^(c) No phosphine added during recycling. ^(d) Solvents degassed and kept under N₂, CO₂ or CO/H₂ at all times, no phosphine added during recycling. ^(e) 0.8 molal additive added.

The retention of the DMEA in the aqueous phase upon protonation by CO₂ was not complete and loss of DMEA to the product phase in each cycle may account for the changing volumes of aqueous phase in successive cycles (FIG. 30, right side images). To minimize loss of the amine to the organic phase, it may be preferable to use polyamines as additives; they generally have better retention in the aqueous phase and can generate solutions of greater ionic strength at lower loadings. However, a polyamine that does not interfere with the reaction should be selected. The conversions observed during hydroformylation of styrene when N,N,N′,N′-tetramethyl-1,4-diaminobutane (TMDAB) was used (see Entry 4 above), while effective, were lower than observed using DMEA. Without wishing to be bound by theory, this may be the a result of the bidentate nature of the TMDAB, which may be competing with TPPTS for positions on the metal, ultimately deactivating the catalyst. The use of better chelating water-soluble phosphines may improve conversions using the polyamine switchable water additives without the resulting loss of catalytic activity.

The leaching of rhodium metal into the organic product phase was observed by ICP-MS (see the table below). Minimal leaching was observed through the first cycle; however upon the second and third cycles, the amount of rhodium lost to the product phase did increase. Despite the increases in rhodium leaching as recycling of the aqueous phase proceeded, the greatest amount of total loss in a single recycling step was never more than roughly 10% of the original amount of rhodium initially used.

The table below shows the concentration of rhodium found in the organic phase, containing products, after separation by switchable water as determined by ICP-MS. Samples were acquired from organic phases noted in Entry 1 of the table above.

Rhodium Concentrations in the Organic Phases^(a) Cycle 1 Cycle 2 Cycle 3 1.07 ± 0.04 mg L⁻¹ 3.63 ± 0.04 mg L⁻¹ 10.12 ± 0.25 mg⁻¹ L ^(a)Average of two runs.

This example demonstrates the successful use of switchable water additives to allow homogeneous catalysis to take place in a monophasic solvent mixture and yet allow the subsequent catalyst/product separation to take place in a biphasic solvent mixture. This method does not suffer from the traditional mass transfer issues that accompany biphasic reactions because the system is monophasic during the catalysis. This method can also tolerate alkenes of lower water solubility than traditional biphasic aqueous/organic catalysis. The hydroformylation reactions performed in switchable water are run at low syn gas pressures, on short timescales, and with facile separation of catalyst from product because of CO₂ induced phase separation. Recycling of the catalyst solution was performed with ease by removing CO₂ from the solution by sparging with an inert gas or air and/or moderate heating. The Rh/TPPTS catalyst maintained good conversion, product selectivity, and regioselectivity after recycling. This method for solving the inherent rate limitations of conventional biphasic catalysis does not require high pressure CO₂ or expensive fluorous or ionic liquid solvents.

Example 30: Solubility of Switchable Water Additives

30.1 Switchable Solubility of Butylated Polyethyleneimine (MW=600)

In a 100 mL round bottom flask equipped with a 1 cm stir-bar, 293 mg of butylated polyethyleneimine (MW=600) was suspended in 50 mL deionized water and stirred for 30 min at room temperature. The solid was allowed to settle for 72 h, then 5 mL of the supernatant was removed and filtered. From the filtered solution, three samples of 1 mL each were placed into round bottom flasks. The water was evaporated and the samples weighed. An average of all three sample weights was taken.

The rest of the solution was treated with CO₂ for 1 hour by bubbling with a single gauge needle (flow rate: 80 ml/min). The mixture turned almost completely clear but some BPEI was still insoluble, hence saturated. Twenty milliliters of the solution was filtered off and three samples of 5 mL each were placed into round bottom flasks. The water was evaporated and the samples weighed. An average of all three samples was taken. An overview of the results is given below.

sample 1 sample 2 sample 3 average solubility 0.33 mg/mL 0.33 mg/mL 0.33 mg/mL 0.33 mg/mL without CO₂ solubility  7.2 mg/mL  7.8 mg/mL  8.4 mg/mL  7.8 mg/mL with CO₂

Replacing CO₂ with argon lead to the formation of a white suspension. Another addition of CO₂ dissolved the polymer again. This process was repeated 3 times.

30.2 Switchable Solubility of Propylated Polyethyleneimine (MW=600)

In a 100 mL round bottom flask equipped with a 1 cm stir-bar, 293 mg of propylated polyethyleneimine (MW=600) was suspended in 50 mL deionized water and stirred for 30 min at room temperature. The solid was allowed to settle for 72 h, then 10 mL of the supernatant was removed and filtered. From the filtered sample, three samples of 3 mL each were placed into round bottom flasks. The water was evaporated and the samples weighed. An average of all three samples was taken.

The rest of the solution was treated with CO₂ for 1 hour by bubbling with a single gauge needle (flow rate: 80 ml/min). The mixture turned completely clear, hence it was below saturation point. 10 mL of the solution was filtered off and three samples of 3 mL each were placed into round bottom flasks. The water was evaporated and the samples weighed. An average of all three samples was taken. An overview of the results is given below.

sample 1 sample 2 sample 3 average solubility  3.3 mg/mL  3.3 mg/mL  3.6 mg/mL  3.5 mg/mL without CO₂ solubility 72.0 mg/mL 72.0 mg/mL 73.0 mg/mL 72.3 mg/mL with CO₂

As all of the polymer dissolved in the presence of CO₂, the actual solubility was higher than 72.3 mg/mL.

Replacing CO₂ with argon lead to formation of a white suspension. Another addition of CO₂ dissolved the polymer again. This process was repeated 3 times.

Example 31: Switchable Water Additive Conductivity Measurements

Solution conductivity measurements were recorded on a Thermo Scientific Orion 5-Star Plus conductivity meter (Fisher Scientific, Ottawa, Ontario, Canada). Ultra pure water (18 MΩ) was obtained using an Elga Lab Water PureLab Flex system (High Wycombe, UK). Tetra-n-butylammonium bromide was purchased from Sigma Aldrich Inc. (Oakville, Ontario, Canada). 3-dimethylamino-1-propylamine was purchased from Alfa Aesar (VWR, Mississauga, Ontario, Canada).

The solution conductivities of the materials given below were measured. The mass of each material indicated was weighed into a 150 mL beaker charged with a stir bar along with 100 mL of ultra pure water. The solutions were stirred until visibly dissolved and their conductivity measured. In the case of both MW=450,000 functionalized and ionic polyacrylic acid samples and the MW=350,000 polymethyl methacrylate sample, gel particles formed, indicating partial solubility. All solutions were left to stir overnight to test reproducibility. Solution conductivities were re-recorded giving little change in values. CO₂ was bubbled at 10 psi through a fine glass frit tube (to make bubble size as small as possible for greater surface area and therefore faster carbonation) with each solution for 30 minutes. In the case of TBAB and functionalized PMMA, significant amounts of bubbling were observed. Solution conductivities were re-recorded.

Initial C C after 30 mins Material Mass (g) (μS/cm) CO₂ (μS/cm) Ultrapure H₂O N/A 1.31 41.2 H₂N(CH₂)₃NMe₂ 0.255 398 3360 [^(n)Bu₄N]Br 0.806 1892 1781 PAA(1,800) 0.180 235 238 Ionic PAA (MW = 1,800) 0.196 398 1107 (1240)^(a) Ionic PAA 0.196 145 750 (MW = 450,000) Neutral Functionalized 0.200 251 818 PAA (MW = 1,800) Neutral Functionalized 0.200 58 334 PAA (MW = 50,000) Neutral Functionalized 0.200 2.07 42.4 PAA (MW = 450,000)^(c) Functionalized PMMA 0.112 201 1086 (MW = 35,000) Functionalized PMMA 0.080^(b) 102 494 (MW = 120,000) Functionalized PMMA 0.112 186 410 (MW = 350,000) ^(a)An aliquot of this solution after this measurement was sealed in a high pressure reactor, pressurized to 130 psi, and stirred for 16 hours at room temperature before solution conductivity measurement was re-measured. This measurement was performed to verify that the procedure described above (30 min, 10 psi CO₂ bubbling) was sufficient to fully switch additive. ^(b)Measurement performed in 80 mL deionized water. ^(c)This polymer sample was observed to have very low solubility in water.

Example 32: Kaolinite Clay Settling Using Switchable Water

Kaolinite clay fines constitute about half of the solid content in oil sands tailing (Ramachandra Rao, S., 1980, “Flocculation and dewatering of Alberta oil sands tailings.” Int. J. Miner. Process., 7 (3), 245-253). Kaolinite, a hydrous aluminum silicate of composition Al₂O₃.2Sio₂.2H₂O (Giese, R., & van Oss, C., 2002, Colloid and Surface Properties of Clays and Related Minerals (Vol. 105), A. Hubbard, Ed. United States of America: Marcel Dekker, Inc.; and Velde, B., 1995, Origin and Mineralogy of Clays. United States of America: Springer-Verlag New York, Inc.), occurs in roughly hexagonal platelets with a length-to-thickness ratio of 10:1 (Michaels, A. a., 1962, “Settling Rates and Sediment Volumes of Flocculated Kaolin Suspensions.” Ind. Eng. Chem. Fundamen., 1 (1), 24-33). Due to the amphoteric property of kaolinite, the faces of the particles possess a permanent negative charge, while the charge on the edge surface is pH-dependent. Under acidic conditions (pH lower than 6) (Michaels, 1962. supra), the aluminum exposed at the edges acquires hydrogen ions from water and assumes a positive charge. The edge and face surfaces then mutually attract, leading to edge-face (E-F) flocculation, and giving form to “card-house” flocs. Under alkaline conditions the edges become neutral or even positively charged, thus disrupting the E-F interactions, providing that electrolyte concentration is low. Increase in electrolyte concentrations, and thus increase in ionic strength of the solution, reduces electrostatic interactions (attractive or repulsive) due to compressed electrical double layer or ion shielding of surface charges. As a result, flocculation primarily occurs between basal surfaces—or face-face (F-F)—forming “card-pack” flocs. The ionic strength effect is independent of solution pH. (Schofield, R., 1954, “Flocculation of kaolinite due to the attraction of oppositely charged crystal faces” Discussions Faraday Soc., 18, 135-145; Michaels, 1962, supra; and Nasser & James, 2006, “Settling and sediment bed behaviour of kaolinite in aqueous media.” Separation and Purification Technology, 51 (1), 10-17).

In this example, the use of a switchable water additive as the flocculating agent is demonstrated. The use of a switchable water additive can enhance water recyclability in oil sands operations by drastically reducing the energy and material demanded by conventional tailing dewatering methods.

Experimental & Materials

Kaolinite Suspension Settling and Supernatant Turbidity

Two separate samples of kaolinite were purchased from Ward's Natural Science and were used as received. Deionized water with a resistivity of 18.2 MΩ·cm (Synergy® UV, Millipore) was used throughout this study. CO₂ (Supercritical Chromatographic Grade, 99.998%, Praxair) was used as received. 100 mL graduated cylinders (Kimble Kimax, single metric scale, 20025H 50) were used for all settling tests. TMDAB was purchased from TCI. Consistency in cylinder dimensions is particularly important, as it has been reported that container height can influence settling rate (Michaels, 1962, supra).

The kaolinite suspension was prepared by adding clay fines to 100 mL of aqueous TMDAB. The effects of changing clay loadings (2.5%, 5%, and 7% w/v) and TMDAB concentrations (blank, 0.01, 0.1, 1, 10 mM) on settling behaviour were investigated. The mixture was stirred with a magnetic stirrer for 15 minutes at 900 rpm prior to transfer to a graduated cylinder. Both “on” (CO₂-treated) and “off” forms of TMDAB were investigated for their effect on settling. For the “on” experiments, CO₂ was bubbled through the mixture in the graduated cylinder using a 20-gauge needle for 1 hour at 100-150 mL/min. The cylinder was then immediately sealed with a rubber septum and bulk settling was monitored over 2 hours with a cathetometer (Eberbach). Supernatant from each of the settling experiments was sampled and its turbidity was measured using a turbidity meter (TB200, Orbeco-Hellige).

Settling Tests to Investigate the Effect of pH and Ionic Strength

The pH of the following 5% (w/v) kaolinite suspensions were measured: CO₂ blank and 1 mM TMDAB and 10 mM TMDAB after CO₂-treatment. To investigate the effect of pH on suspension settling behaviour, 5% (w/v) kaolinite suspensions were prepared, and the pH of each suspension was adjusted with HCl and NaOH to match the pH of corresponding treatment conditions. To investigate the effect of ionic strength on suspension settling behaviour, pH was again corrected to match the pH of corresponding treatment conditions, and ionic strength was adjusted with NaCl or ammonium sulphate, assuming all basic sites on the diamine were protonated.

Particle Size and Zeta Potential Measurements

Particle size and zeta potential were measured using Zetasizer Nano ZS (Malvern). 25 mg of clay fines (kaolinite and montmorillonite) were added to 10 mL of deionized water. A suspension was created using a vortex. All CO₂ treatments were conducted for 1 hour. The pH was adjusted with HCl and NaOH.

Results & Discussion

The Effect of TMDAB on Kaolinite Suspension Behaviour

Kaolinite and montmorillonite clays fines naturally form a stable aqueous colloidal suspension. The presence of TMDAB in suspension in the “off” form did not have any observable effect on particle flocculation and settling and maintained a stable suspension. However, upon introduction of CO₂ to turn on TMDAB, settling was observed in a concentration-dependent manner, as presented in FIG. 31. The settling profiles are plotted as the percent column height of the interfacial plane between the slurry and the supernatant as a function of time. Increasing TMDAB concentration lead to slower settling rates. The upper limit of settling rate was characterized by a CO₂-treated suspension with no TMDAB. At 0.1 mM and 0.01 mM TMDAB (not shown) the settling profiles were not different from that of the CO₂-treated suspension without additive. CO₂ alone can facilitate bulk settling in a clay colloid. In fact, it is already an industrial practice of Canadian Natural Resources Limited to inject CO₂ into tailing ponds to accelerate the settling of tailing fines. CO₂ forms carbonic acid in water and thereby lowers the pH. Low pH promotes clay particle flocculation and the subsequent settling.

While settling rate was the most rapid in a CO₂-treated suspension without TMDAB, it resulted in the most turbid supernatant; as the concentration of TMDAB increased, the turbidity of the supernatant decreased (FIG. 32). However, at high concentrations (100 mM), the presence of oxidized amine became significant and imparted a yellowish tinge in the supernatant. Thus, an important design consideration is a compromise between desirable settling rate and acceptable water turbidity. 1 mM TMDAB was required to reduce the supernatant turbidity by a significant amount. A photographic time-profile of the settling of a kaolinite suspension treated with 10 mM TMDAB and CO₂ is presented in FIG. 33. The clarity in the supernatant and the sharp sediment line suggest that flocs were formed with comparable size and density (Michaels, 1962, supra). FIG. 34 illustrates the supernatant turbidity at different treatment conditions and colouration at 100 mM TMDAB.

Zeta potential is a simple method to predict colloidal system stability (Delgado, A., González-Caballero, F., R. Hunter, L. K., & Lyklema, J. (2005). Measurement and Interpretation of Electrokinetic Phenomena. Pure Appl. Chem., 77 (10), 1753-1805). At large absolute zeta potential values, the particles are highly charged and repel one another. This prevents the particles from flocculating, and thus results in a stable suspension. Flocculation begins to take place at a critical value around −30 mV. (Everett, D. (1988). Basic Principles of Colloid Science. London, England: Royal Soceity of Chemistry) The closer zeta potential is to zero, the more it indicates weakened repulsive forces, which allows the particles to flocculate under attractive van der Waals forces. FIG. 35 shows the zeta potentials of clay particles under different treatment conditions. A kaolinite colloid without treatment or with the “off” form of TMDAB generally exhibited zeta potential values in the stable range. This was consistent with the suspension settling experiments, as no settling was observed under these two conditions. The zeta potential of a CO₂-treated suspension with no additives indicated some flocculation and destabilization of the system; however, only to a minimal extent. This was also consistent with the settling test: while settling did occur, the supernatant was turbid. The “on” form of 1 mM TMDAB was able to significantly lower the zeta potential of the suspension components. This was once again reflected in the settling of clay and a much clearer supernatant.

Aggregate size can serve as an indication of flocculation. While aggregate size is not a fundamental property of a flocculated suspension, it is a dynamic property of the effective collisions that contribute to aggregation (Michaels, 1962, supra). FIG. 36 illustrates that particle size measurements exhibited a similar trend to zeta potential measurements under the same set of treatment conditions. No notable increase in particle size was evident in the presence of the “off” form of TMDAB or even under CO₂ treatment. However, the particle size in the TMDAB-CO₂ treated suspension was approximately double that of the suspension particles under no treatment. Particle size is only a crude indication of flocculation, since naturally occurring clay particles exhibit a wide range of sizes, as indicated by the PDI of these samples.

The Effect of Clay Loading on Kaolinite Suspension Settling Behaviour

Kaolinite clay loading level can influence the suspension settling characteristics. Settling rate decreased as clay loading increased, as shown in FIG. 37. This was consistent with the findings reported by Michaels and Bolger (Michaels, 1962, supra). The supernatant turbidity was also sensitive to clay loading in CO₂-treated suspensions: turbidity increased significantly with increasing clay loading (FIG. 38). However, this loading-dependent effect on turbidity was not observed in suspensions treated with 1 mM TMDAB and CO₂. TMDAB exerted a much stronger effect on clay behavior in suspension, which overcame the influence of clay loading level.

The Effect of pH and Ionic Strength on Kaolinite Suspension Behaviour

To investigate whether the TMDAB-induced effect on kaolinite suspension was predominately driven by solution pH effect or ionic strength effect, settling tests were conducted with suspensions adjusted to have pH and/or ionic strength that corresponded to CO₂-treated TMDAB suspensions. All pH and ionic strength suspension settling tests were conducted with kaolinite sample 2 (see below).

The pH of kaolinite suspensions under different treatment conditions was measured and shown in Table A. Kaolinite clay particles were shown to have acidic properties in an aqueous environment. Three suspensions were each adjusted to have the same pH as a suspension that was CO₂ treated (1), 1 mM TMDAB-CO₂ treated (2), or 10 mM TMDAB-CO₂ treated (3). Settling was observed in 1 and 2 but not 3. The bulk settling for 1 and 2 exhibited comparable profiles. The supernatant turbidity of 2, however, was significantly higher than that of 1 (Table 2). Low pH was favourable for kaolinite flocculation. An increase in solution pH became increasingly unfavourable until settling was no longer observed. Michaels and Schofield had reported that under pH 6 kaolinite particles could attract electrostatically and form “card-house” flocs. This electrostatic attraction is lost with increasing pH. (Michaels, 1962, supra; and Schofield, R., 1954, “Flocculation of kaolinite due to the attraction of oppositely charged crystal faces.” Discussions Faraday Soc., 18, 135-145). While pH exerted an effect on suspension behavior, in particular supernatant turbidity, bulk-settling rate was independent of solution pH.

Zeta potentials of 1, 2, and 3 all measured below the critical value, with 3 being significantly higher.

TABLE A pH Sample 1 Sample 2 No treatment 5.35 4.90 CO₂ — 4.25 1 mM TMDAB — 7.13 1 mM TMDAB + CO₂ — 4.75 10 mM TMDAB — 10.41 10 mM TMDAB + CO₂ — 5.95

TABLE B Corresponding Supernatant turbidity Study pH treatment (NTU) 1 4.25 CO₂ Blank  64 2 4.75 1 mM TMDAB + CO₂ 520 3 5.95 10 mM TMDAB + CO₂ NO SETTLING

TMDAB in its “off” form acted as a base and elevated suspension pH in a concentration-dependent manner, as illustrated in Table A. Since it has been shown that settling does not occur at high pH, it is reasonable that no settling was observed in suspensions treated with the “off” form of TMDAB.

A discrepancy in supernatant turbidity was observed between the 2 samples of kaolinite in suspensions treated with CO₂ in FIG. 32. The supernatant turbidity that resulted from sample 2 was significantly lower than that which resulted from sample 1 under the same treatment condition. Without wishing to be bound by theory, the discrepancy could be explained by the pH effect and differences in particle size. Sample 2 was more acidic than sample 1 in an aqueous environment (Table A); thus, a suspension created with sample 2 treated with CO₂ was at a lower pH than a suspension similarly created with sample 1. The difference in pH was likely enough to result in the observed differences in supernatant turbidity. Furthermore, FIG. 36 indicates that sample 2 particle sizes were on average larger than sample 1 particles. Larger particle sizes lead to more pronounced Van der Waals attractions and larger influence by gravitational pull; thus, a suspension of larger particles settles more uniformly and rapidly.

While pH was found to influence the ability of clay particles to settle, the pH effect failed to explain why an increase in TMDAB concentration lead to a decrease in both settling rate and turbidity. Ionic strength, another known factor in suspension settling, was investigated as a potential mechanism through which TMDAB works. For a given amine additive (denoted B) with n basic sites, the fate of the aqueous amine in the presence of CO₂ is illustrated by Equation (1): B+nH₂O+nCO₂→BH_(n) ^(n+) +nHCO₃ ⁻  (1)

Assuming all basic sites are protonated, the ionic strength, then, switches from zero to ½m(n²+n), as illustrated by Equation (2): I=½m(+n)²+½mn(−1)²=½m(n ² +n)  (2) where m is the molality of the additive.

TMDAB has two basic sites. Upon CO₂-treatment, ionic strength of aqueous TMDAB thus switches from zero to 3 m. For each of the CO₂ treated 1 mM TMDAB and 10 mM TMDAB solutions, a suspension was created with identical pH and ionic strength as its TMDAB-treated counterpart. pH was adjusted with HCl and NaOH. Ionic strength was adjusted with NaCl to reproduce the ionic strength imparted by 1 mM and 10 mM TMDAB (4 and 5 respectively) or ammonium sulphate (hereafter AS) for the same set TMDAB treatments (6 and 7). Both 4 and 6 resulted in comparable settling profiles as a suspension treated with 1 mM TMDAB and CO₂ (FIG. 39). While corrected pH alone (3) was inadequate in promoting settling, 5 and 7 were able to bring about similar settling profiles to a suspension treated with 10 mM TMDAB and CO₂ (FIG. 40). It is likely that settling rates can be influenced by both pH and ionic strength. Higher concentrations of TMDAB impart both increased pH and ionic strength; high pH impedes settling while high ionic strength does the opposite. This could explain the observed decrease in settling rate that accompanied the increase in TMDAB concentration.

The supernatant turbidity measurements from pH and ionic strength settling tests further show that ionic strength is an important factor in reducing turbidity, as illustrated in FIG. 41.

Zeta potential measurements indicated that neither pH nor ionic strength gave an adequate explanation of the behaviour brought about by CO₂-treated aqueous TMDAB on a microscopic level in terms of electrical double layer activities. Although the addition of electrolyte successfully decreased zeta potentials in comparison to the absence of electrolyte, increasing the concentrations of electrolyte (at corresponding pH) did not produce the same trend as increasing TMDAB concentration (FIG. 41). However, an increase in particle size was observed at higher concentrations of electrolyte, which is consistent with the trend in particle size with increasing TMDAB concentration (FIG. 42). pH alone was unable to produce the particle size trend imparted by TMDAB.

Corresponding Particle size pH Treatment z-avg (d · nm) PDI 4.90 No treatment — — 4.25 CO₂ 980 0.202 4.75 1 mM TMDAB + CO₂ 939 0.305 5.95 10 mM TMDAB + CO₂ 858 0.011

Corresponding Particle size pH I (mM) Treatment z-avg (d · nm) PDI 4.75 3 1 mM TMDAB + CO₂ 1092 0.247 5.95 30 10 mM TMDAB + CO₂ 1556 0.195

Thus, it appears that while pH and ionic strength are both important factors that affect clay suspension behavior, and ionic strength is likely the predominant mode of action through which TMDAB operates.

Example 33: Effect of Switchable Additives on Colloidal Interactions Found in Oil Sands and Measured by Chemical Force Spectrometry

In this study, adhesion forces between bitumen and mineral surfaces were modeled and studied by chemical force spectrometry (CFS), particularly to demonstrate how switchable additives can be used to control these interactions, which are crucial to the bitumen liberation phase of the oil sands extraction process. Two organic functional groups commonly found in bitumen were selected to represent the bitumen: an aromatic phenyl group and a carboxylic acid group. Self assembled monolayers (SAM) terminated with these functional groups were formed on gold coated AFM tips for CFS experiments. The mineral substrates investigated include mica and silica, which are components of real oil sands systems (Takamura, K. Can. J. Chem. Eng. 1982, 60, 538. Gupta, V.; Miller, J. D. J. Coll. Inter. Sci. 2010, 344, 362-371). While clays such as kaolinite and montmorillonite are, like mica, sheet-like aluminosilicates and are found in oil sands, these minerals proved to be unusable in the chemical force experiments, due to extensive swelling in aqueous solution. Tip/sample interactions were analyzed as a function of pH, in the presence of divalent cations (e.g. Ca²⁺, as used during the industrial process), and in the presence of switchable additives. As described above, CO₂ switchable chemistry is mediated by changes in solution pH due to the dissolution of CO₂ and the formation of carbonic acid. Thus, further measurements to determine the effects of solution pH on the interactions between SAM and mineral substrate, in the absence of switchable surfactant, were carried out. The literature related to oil sands chemistry indicates that divalent cations decrease bitumen recovery through the promotion of adhesion between the bitumen and sand moieties. The divalent cation both collapses the electrical double layer and shields the two negatively charged surfaces to increase adhesion (Iler, R. K. Chemistry of Silica-Solubility, Polymerization, Colloid and Surface Properties and Biochemistry; John Wiley & Sons, Hoboken U.S.A., 1979; and Maslova, M. V.; Gerasimova, L. G.; Forsling, W. Colloid J. 2004, 66, 322). Calcium sulfate, a common additive to oil sands tailings, was used in the CFS studies to demonstrate how our model systems serve in mimicking real oil sands systems.

Experimental

Synthetic Methods

The synthesis of 12-phenyldodecanethiol was accomplished using previously published literature methods (Lee, S.; Puck, A.; Graupe, M.; Colorado Jr., R.; Shon, Y. S.; Lee, T. R.; Perry, S. S. Langmuir 2001, 17, 7364; Speziale, J. Org. Syn. Coll. 1963, 4, 396; and Frank, R.; Smith, P. J. Am. Chem. Soc. 1946, 68, 2103). The ¹H-NMR, ¹³C-NMR and mass spectra (high res, El⁺) matched those reported in the literature (Lee, S. 2001, supra). NMR and MS spectra showed that the product was a mixture of the thiol and the corresponding disulfide (3:1 ratio by ¹H-NMR) due to partial oxidation during the synthesis. However, it has been demonstrated in the literature (Nuzzo, R.; Allara, D. J. Am. Chem. Soc. 1983, 105, 4481; and Bain, C.; Bieyuck, H.; Whitesides, G. Langmuir 1989, 5, 723) that disulfides also self assemble onto gold surfaces through scission of the sulfur-sulfur bond. Therefore, this material can still be used to create the desired self-assembled monolayers on gold.

N′-alkyl-N,N-dimethylacetamidines C4 and C8 were also synthesized by previously published literature methods (Liu, Y.; P. G. Jessop, M. Cunningham, C. Eckert, C. Liotta. Science 2006, 313, 958). 12-Mercaptododecanoic acid was purchased from Sigma Aldrich and used as received.

Silicon (111) wafers were purchased from Virginia Semiconductors Inc. These substrates were cleaned and oxidized with piranha solution (3:1 concentrated H₂SO₄: 35 wt % H₂O₂ in H₂O) for 1 hour prior to being thoroughly rinsed with deionized water and dried under a stream of N₂(g).

Muscovite mica (V-4 grade, SPI) was freshly cleaved prior to use. Double sided tape was adhered to the surface and subsequently pulled off to reveal a new basal surface for AFM force measurements.

Instrumentation

AFM force-distance curves were obtained using a PicoSPM instrument (Molecular Imaging, Tempe, Ariz.) and a Nanoscope IIE controller (Digital Instruments, Santa Barbara, Calif.). All experiments were conducted at 25° C.

Gold-coated silicon nitride AFM tips (CSC-38, MikroMasch USA; spring contant k=0.08 N/m; tip radius <10 nm, as per manufacturer's specifications) were functionalized for adhesion force measurements by submerging the tips in a 1×10⁻³ M solution of 12-phenyldodecanethiol (“phenyl tip”) or 12-mercaptododecanoic acid (“acid tip”) in isopropanol for 24 h. Force measurements were conducted under aqueous conditions in solutions prepared using deionized water (18.2 MΩ, Millipore). The adhesive force between the tip and the sample was determined from measuring the well depth of over 1000 force distance curves under each experimental condition. The adhesion force was measured approximately 200 times at different surface sites. At least 5 surface sites were tested for each experimental condition, but typically 15-20 sites were studied. At least 2 different tips were used in these measurements. The large number of measurements was conducted to obtain a more representative value of adhesion between the tip and the sample. The reported values are an average of all the measured adhesive forces and the errors are the calculated 95% confidence intervals.

The chemical force titration experiments were conducted using freshly prepared unbuffered aqueous solutions of pH ranging from 3 to 11. To modify the pH, addition of 1.0 M NaOH solution was used to achieve alkaline conditions and similarly a 1.0 M HCl solution was added to achieve acidic conditions. Unbuffered pH solutions were used to prevent unwanted interactions between the surface and the ionic species associated with the buffer. The pH values were checked before and after the experiment and the solutions were changed frequently to minimize changes in pH due to the dissolution of atmospheric CO₂. Experiments were carried out under low ionic strength conditions and the only ions introduced into the system were from the use of HCl and NaOH for pH adjustment.

For experiments involving CO₂ saturated solutions, the solutions were pretreated with CO₂ prior to acquiring the force curves. Ultra pure CO₂ (Supercritical CO₂ Chromatographic Grade, Praxair) was bubbled through the solutions using a syringe for 30 min. For these force measurements, the AFM was outfitted with an environmental cell that was filled with CO₂ to maintain a CO₂ atmosphere around the aqueous solutions during the experiment.

Results and Discussion

When switchable additives are activated or deactivated through the addition or removal of CO₂ from the system, the solution pH is varied. Chemical force titration profiles (plots of tip/sample adhesion as a function of pH) were measured for AFM tips functionalized using both phenyl- and carboxylate-terminated SAM's with mica and silica substrates. These experiments were an important control case to monitor the background effect of any solution pH changes. The chemical force titration profiles for the silica substrate and the acid and phenyl terminated AFM tips are shown in FIG. 43A. Note that the forces measured between silica substrate and the acid tip were scaled by a factor of 10 relative to the remaining data in FIG. 43A.

The maximum adhesion force of 0.18±0.04 nN was measured at pH 4 in the chemical force titration profile between the acid tip and the silica substrate. The adhesion force dropped off rapidly at higher and lower pH values, which is similar to force titration profiles previously observed in systems where the tip and sample interactions are dominated by hydrogen bonding forces (van der Vegte, E. W.; Hadziioannou, G. J. Phys. Chem. B 1997, 101, 9563; and van der Vegte, E. W.; Hadziioannou, G. Langmuir 1997, 13, 4357). The surface pK_(a) of the acid-terminated SAM has been previously observed to be at approximately 4-5, consistent with the 4.9 pK_(a) of long-chain alkanoic acids in water. Assuming that the silica substrate is negatively charged over much of the pH range studied, a large number of ionic H-bonds may form at or below the surface pK_(a) of the tip, leading to the strong interactions observed in this pH range. At pH values above the pK_(a), the adhesion force diminished sharply with increasing pH, as would be expected because the tip is becoming increasingly negatively charged and it is interacting with a negatively charged substrate. Interestingly, the adhesion force increased again slightly at pH 11. This was a reproducible trend, seen in independent experiments. A possible explanation may be the increase in Na⁺ concentration from the increase in NaOH required to achieve this high pH. Both the silica substrate and the acid tip are expected to be negatively charged at pH 11 and the presence of Na⁺ cations may serve to screen the two negatively charged surfaces. A maximum adhesion force of 1.7±0.4 nN for the phenyl-terminated AFM tip and the silica substrate was observed at pH 7. The chemical force titration profile shows that the adhesion force decreased gradually at higher and lower pH values. This result is consistent with hydrophobic forces dominating the tip-sample interaction.

The chemical force titration profiles for the mica substrate and the acid- and phenyl-terminated AFM tips are shown in FIG. 43B. As with the silica substrate, a maximum adhesion force (1.6±0.2 nN) between the acid tip and the mica substrate was observed at a pH of 4. This trend may also be attributed to hydrogen bonding interactions between the substrate and tip with a similar mechanism as outlined above. Adhesion forces between phenyl-terminated tip and mica substrate were weak through the entire pH range (FIG. 43B). Again, hydrophobic interactions appear to be a main contributing factor in the tip-sample interaction.

In subsequent CFS experiments, the cationic switchable surfactant, C8 (FIG. 44), was compared with C4, an amidine with a four carbon chain tail (FIG. 45). Unlike C8, C4 is not a surfactant molecule in the presence of CO₂ due to its short alkyl chain length. However, both C4 and C8 can be protonated in aqueous solutions saturated with CO₂ to yield a positively charged amidinium head group. Thus, comparison of C4 and C8 determines to what extent changes in adhesion force may be attributed to the surfactant properties or simply due to the presence of the protonatable amidine functionality and consequent increase in ionic strength following protonation.

The results from the CFS experiments in the presence of C4 are presented below.

Adhesion Force (nN) Carboxylic Acid- terminated tip Phenyl-terminated tip Additive Silica Mica Silica Mica 1 mM C4 0 0.01 ± 0.01 0 0.01 ± 0.01 (pH 11 ± 0.2) 1 mM C4 + 0.18 ± 0.04 1.58 ± 0.18 0.07 ± 0.02 0.74 ± 0.35 CO₂ (pH 5 ± 0.2) 1 mM C8 0.39 ± 0.20 0.23 ± 0.28 0.97 ± 0.33 1.97 ± 0.19 (pH 11 ± 0.2) 1 mM C8 + 1.53 ± 0.19 1.94 ± 0.23 1.05 ± 0.38 0.41 ± 0.20 CO₂ (pH 5 ± 0.2) pH 11 ± 0.2 0.10 ± 0.04 0 0.64 ± 0.09 0 NaOH Modified pH 5 ± 0.2 0.08 ± 0.05 0.31 ± 0.30 0.36 ± 0.26 0.35 ± 0.46 HCl Modified

A consistent trend was observed for all four tip/sample pairs. In the absence of CO₂, there was no interaction measured between the tip and the surface. Upon saturation of the aqueous solution with CO₂, the adhesion force increased dramatically.

Because the pH of solution changes due to addition of CO₂, the table also shows the adhesion forces observed in the absence of the switchable amidine, but at the same pH (using HCl or NaOH). For three of the four tip/sample pairs, the increase in adhesion force that was observed in the presence of C4 was greater than when the solution pH was modified by HCl or NaOH, and in one pair (carboxylate/mica) the increase was dramatically greater. The observed modifications in adhesion force cannot be attributed to pH changes alone.

The table also shows a similar set of data using C8, the active surfactant species. The addition of CO₂ to the C8 solution caused a dramatic rise in the attractive force for the carboxylate-terminated tip, but not for the phenyl-terminated tip. Again, the changes induced were greater than what may be attributed to changes in pH alone. Unlike the C4 case, the presence of C8 lead to significant adhesion forces for all four tip-sample pairs regardless of the presence or absence of CO₂.

The results from the CFS experiments suggest a mechanism by which amidines such as C4 and C8 can reversibly control adhesion between the various components of an oil sand. They also show that such amidines may be potentially useful as additives for the reversible manipulation of the water chemistry in oil sands extraction. In aqueous solutions containing these additives without CO₂, the adhesion forces between the organic functionalized tips and the mineral surfaces were minimal. This suggests that this additive may be useful for decreasing adhesion between bitumen and mineral surfaces, thus facilitating bitumen liberation and flotation during the separation stage of oil sands processing.

Gold-coated AFM tips functionalized with 12-mercaptododecanoic acid or 12-phenyldodecanethiol were used as models of bitumen surfaces for a study of adhesive interactions between these model bitumen surfaces and mica or silica. The parameters investigated included variations in pH, changes in calcium sulfate concentration, addition of amidine additives C4 and C8, and the presence or absence of CO₂. In the chemical force spectrometry experiments involving C4, the adhesion forces between the organic functionalized AFM probes and the mineral substrates were low in the absence of CO₂, but an increase in adhesive interaction was observed when in the presence of CO₂. The same trend was observed with experiments involving C8, but only when the acid tip was used. The lack of a CO₂-triggered increase for the phenyl tip may be due to the hydrophobic tail of C8 being attracted towards the phenyl tip.

Of the two switchable additives studied, C4 was most consistent in switching on and off the adhesion interactions between all of the organic and mineral pairs, while C8 only showed that effect with the carboxylic acid tip. This suggests that C4 can be useful for facilitating bitumen and mineral separation in the extraction phase of the industrial process.

Example 34: Titanium Oxide Settling with Switchable Water Additives

This titanium oxide settling study was used as a model for waste water treatment to remove unwanted particulates using a switchable additive.

The titanium(IV) oxide (nanopowder, ˜21 nm particle size, ≥9.5% trace metals basis) used was purchased from Sigma-Aldrich.

In this study 0.050 g of 3-(dimethylamino)-1-propylamine functionalized PMMA (MW=120,000) was placed into two different 250 mL round bottom flasks equipped with a 2 cm Teflon stir-bar. 100 mL deionized water was added and the solutions were stirred (600 rpm) until the polymer dissolved (10 min to 16 h). Then 1 g of titanium(IV) oxide was added. Both suspensions were stirred at 600 rpm for 1 h, while CO₂ was bubbled through one of the solutions using a gas dispersion tube. After that, both suspensions were transferred into 100 mL graduated cylinders and the settling rate was monitored over time. In the presence of CO₂ very quick bulk settling was observed in the presence of CO₂, leaving a turbid supernatant behind that cleared up within 2 h. Without CO₂ present no settling was observed, resulting in a stable suspension. The supernatant in the presence of CO₂ was only slightly turbid, whereas without CO₂ the supernatant consisted of a stable suspension that was not transparent at all. These results support the use of the switchable additive in a waste water treatment process.

All publications, patents and patent applications mentioned in this Specification are indicative of the level of skill of those skilled in the art to which this invention pertains and are herein incorporated by reference to the same extent as if each individual publication, patent, or patent applications was specifically and individually indicated to be incorporated by reference.

It will be understood by those skilled in the art that this description is made with reference to the preferred embodiments and that it is possible to make other embodiments employing the principles of the invention which fall within its spirit and scope as defined by the claims appended hereto. All such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. 

We claim:
 1. A system for modulating an osmotic gradient across a membrane comprising: a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive is water-miscible or water soluble and includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water; wherein the additive is a polymer, and wherein the at least one functional group is an amine; a source of an ionizing trigger, wherein the ionizing trigger ionizes the at least one functional group in the additive and thereby increases the ionic strength of the switchable water; and a semi-permeable membrane that is selectively permeable for water, wherein the switchable water contacts a first side of the semi-permeable membrane, and a feed stream contacts a second side of the semi-permeable membrane; wherein the system modulates the osmotic gradient across said membrane via modulating the ionic strength of the switchable water.
 2. The system of claim 1, wherein the feed stream comprises: (i) undesirable solutes or particles; (ii) salt and/or minerals; or (iii) a dilute aqueous solution.
 3. The system of claim 2 wherein the feed stream is seawater, brackish water, or wastewater.
 4. The system of claim 1, wherein the system additionally comprises a source of a non-ionizing trigger wherein the non-ionizing trigger neutralizes the at least one functional group ionized by the ionizing trigger and thereby switches the additive from the second form to the first form.
 5. The system of claim 4, wherein the non-ionizing trigger is (i) heat, (ii) a flushing gas, (iii) a vacuum or partial vacuum, (iv) agitation, (v) a strong base, or (vi) any combination thereof.
 6. The system of claim 1, wherein the amine nitrogen has a conjugate acid with a pKa in a range from about 6 to about 14, such that the nitrogen is protonated when the polymer is in the presence of an ionizing trigger.
 7. The system of claim 6, wherein the pK_(a) is in a range from about 8 to about
 10. 8. The system of claim 6, wherein the ionizing trigger is a Brønsted acid, or a gas that when dissolved in water reacts with water to liberate hydrogen ions.
 9. The system of claim 8, wherein the Brønsted acid is hydrochloric acid, formic acid, sulfuric acid or carbonic acid.
 10. The system of claim 6, wherein the ionizing trigger is CO₂, NO₂, SO₂, SO₃, CS₂, or COS.
 11. The system of claim 1, wherein the polymer is insoluble in water when in the first form.
 12. The system of claim 1, wherein the polymer is at least partially soluble in water when in the first form.
 13. The system of claim 1, wherein the polymer is: a biopolymer or a derivative thereof; a functionalized branched or linear polyethyleneimine; a functionalized polymethyl methacrylate (“PMMA”) based polymer; a functionalized polyacrylic acid (“PAA”) polymer; an amine-containing polyacrylic acid salt; a functionalized poly(methyl methacrylate-co-styrene) (“PMMA/PS”); a polymer synthesized from amine-containing monomers; or any combination thereof.
 14. The system of claim 1, wherein the system additionally comprises an apparatus to separate the additive from the water in said switchable water.
 15. The system of claim 14, wherein the apparatus comprises a reverse osmosis system.
 16. The system of claim 14, wherein the first form of the switchable additive is immiscible in water and wherein the apparatus comprises a decanter to decant the first form of the additive from the water.
 17. The system of claim 14, wherein the first form of the switchable additive is insoluble in water and wherein the apparatus comprises a centrifuge, a filter, a skimmer, or a nanofilter to remove the insoluble first form of the additive.
 18. A method for removing a solute from an aqueous solution or concentrating a dilute aqueous solution, comprising the steps of: (a) contacting a switchable water comprising water and an additive switchable between a first form and a second form, wherein said second form of the additive is water-miscible or water soluble and includes at least one ionized functional group that is neutral in said first form of the additive, such that switching the additive from the first form to the second form increases the ionic strength of the switchable water, with an ionizing trigger to ionize at least one functional group in the additive and thereby increase the ionic strength of the switchable water; wherein the additive is a polymer and wherein the at least one functional group is an amine; (b) providing a semi-permeable membrane that is selectively permeable for water and has on one side a draw solution that comprises said switchable water, wherein the step of contacting the switchable water with the ionizing trigger to switch the additive to the second form is performed before or after association of the switchable water with the semi-permeable membrane to increase the osmotic pressure of the draw solution; (c) contacting the other side of the semi-permeable membrane with a feed stream of the aqueous solution to permit water to flow from the aqueous solution through the semi-permeable membrane into the increased ionic strength draw solution; and (d) optionally, removing the additive from the resulting diluted draw solution.
 19. The method of claim 18, wherein the solute is a salt.
 20. The method of claim 19, wherein the feed stream is an aqueous salt solution, such as brackish water or sea water.
 21. The method of claim 18, wherein the feed stream is waste water.
 22. The method of claim 18, wherein step (d) comprises contacting the diluted draw solution with a non-ionizing trigger to switch the additive to its first form.
 23. The method of claim 18, wherein step (d) comprises reverse osmosis.
 24. The method of claim 22, wherein the first form of the switchable additive is immiscible in water and step (d) additionally comprises decanting the first form of the additive from the water.
 25. The method of claim 22, wherein the first form of the switchable additive is insoluble in water and step (d) additionally comprises removing the insoluble first form of the additive from the water.
 26. The method of claim 18, wherein the ionizing trigger is a Brønsted acid, or a gas that when dissolved in water reacts with water to liberate hydrogen ions.
 27. The method of claim 18, wherein the ionizing trigger is CO₂, NO₂, SO₂, SO₃, CS₂, or COS.
 28. The method of claim 26, wherein the Brønsted acid is hydrochloric acid, formic acid, sulfuric acid or carbonic acid.
 29. The method of claim 18, wherein the amine nitrogen has a conjugate acid with a pK_(a) in a range from about 6 to about
 14. 30. The method of claim 29, wherein the pK_(a) is in a range from about 8 to about
 10. 31. The method of claim 18, wherein the polymer is: a biopolymer or a derivative thereof; a functionalized branched or linear polyethyleneimine; a functionalized polymethyl methacrylate (“PMMA”) based polymer; a functionalized polyacrylic acid (“PAA”) polymer; an amine-containing polyacrylic acid salt; a functionalized poly(methyl methacrylate-co-styrene) (“PMMA/PS”); a polymer synthesized from amine-containing monomers; or any combination thereof.
 32. The method of claim 18, wherein the polymer is insoluble in water when in the first form.
 33. The method of claim 18, wherein the polymer is at least partially soluble in water when in the first form.
 34. The method of claim 22, wherein the non-ionizing trigger is (i) heat, (ii) a flushing gas, (iii) a vacuum or partial vacuum, (iv) agitation, (v) a strong base, or (vi) any combination thereof.
 35. The system of claim 6, wherein the ionizing trigger is CO₂.
 36. The method of claim 20, wherein the aqueous salt solution is brackish water or sea water.
 37. The method of claim 25, wherein removing the insoluble first form of the additive from the water comprises centrifugation, filtration, or nanofiltration.
 38. The method of claim 18, wherein the ionizing trigger is CO₂. 